Effect of the coordination centers and the solvents on the parameters of the 1H and 13C NMR spectra of biology active Zn+2 and Cd2+ acetate mononuclear complexes with chelating 1,10- phenanthroline

Effect of the coordination centers and the solvents on the parameters of the 1H and 13C NMR spectra of biology active Zn+2 and Cd2+ acetate mononuclear complexes with chelating 1,10- phenanthroline | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Effect of the coordination centers and the solvents on the parameters of the 1 H and 13 C NMR spectra of biology active Zn +2 and Cd 2+ acetate mononuclear complexes with chelating 1,10- phenanthroline Viktor Demidov, Alexandra Ivanova, Irina Tsvetkova, Vadim Voschikov, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4553203/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The NMR 1 Н and 13 С spectra of Zn + 2 and Cd 2+ acetate mononuclear complexes with 1,10-phenanthroline M(phen) n (OAc) 2 •2H 2 O (M = Zn 2+ and Cd 2+ , n = 1–3) for their solutions in DMSO-d 6 , D 2 O and mixture DMSO-D 6 –D 2 O were studied. The effect of the coordination centers and the solvents on the parameters of the 1 H and 13 C NMR spectra is considered. It is noted that the chemical shifts of the δ H protons of the heteroaromatic rings of 1,10-phenanthroline are sensitive to coordination with Zn + 2 and Cd 2+ ions, but the type of solvent has the greatest effect on the δ Н . For M(phen) n (OAc) 2 •2H 2 O (n = 1,2) complexes, the maximum shift to a weak field of δ H values occurs for the mixed solvent DMSO-D 6 –D 2 O. For complexes [M(phen) 3 ](OAc) 2 •2H 2 O in the mixed solvent DMSO-D 6 –D 2 O, on the contrary, there is a very weak shift of the values of δ H in a strong field compared with the values for DMSO-D 6 and in a weak field compared with the values in D 2 O. The difference in the 1 H NMR spectral pattern for compounds M(phen) n (OAc) 2 •2H 2 O (n = 1,2) and [M(phen) 3 ](OAc) 2 •2H 2 O should be associated with the coordination saturation of the latter, for which the insertion of a solvent – D 2 O or DMSO-D 6 into the internal coordination sphere is practically impossible While the complexes M(phen) n (OAc) 2 •2H 2 O (n = 1,2) are coordination-unsaturated structures and allow solvent molecules to penetrate into their internal coordination sphere. Complexes of Zn + 2 and Cd 2+ with 1,10-phenanthroline were synthesized by complexation reactions. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 1 Introduction Acetate 1,10-phenanthroline complexes are the precursors of the compounds of the new apo-1,10-phenanthrocyanine class systematically studied by us: metallo-N-heterobiphenylenes – glassy electron-rich binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) L n (phen) m M(µ-N-biphen)M(phen) m L n (OAc) l of d-elements ( M ) Zn 2+ [Ar]3d 10 , Cd 2+ [Kr]4d 10 , Co 2+ [Ar]3d 7 , Mn 2+ [Ar]3d 5 , Ni 2+ [Ar]3d 8 , Cr 3+ [Ar]3d 3 (phen = 1,10-phenanthroline, L – amine ligands, OAc - – acetate groups) [1–3]. In their structure, compounds of the new class contain bridging chromophores – pharmacophore ligands of µ-N-biphen , which are characterized by the presence of temperature-accessible lowest electronic biradical triplet states T low . [4–6]. We have established that mononuclear 1,10-phenanthroline acetates of Zn 2+ , Cd 2+ , Co 2+ and Mn 2+ exhibit strong biocidal properties. They effectively inhibit some micromycete fungi. In this work, the NMR spectra of 1 H and 13 C mononuclear 1,10-phenanthroline acetate compounds of Zn 2+ and Cd 2+ were studied in order to use the data obtained to analyze similar spectra of binuclear complexes of a new class – N-heterobiphenylenes. Mononuclear coordination compounds of Zn 2+ with 1,10-phenanthrolines have recently been investigated as potential antibacterial, antifungal and antitumor agents [7]. Interest in metallo-medicinal agents is increasing due to the growing resistance of bacteria, fungi and tumors to the action of antibiotics and traditional drugs [8, 9]. Mononuclear complexes of d-elements with 1,10-phenanthroline derivatives occupy an important place among such agents [10]. Cd 2+ complexes inhibiting the growth of tumor cells are of interest as active potential drugs in antitumor therapy [11]. It is known that many metal ions play a very important role in the biological processes of many living organisms. Zn 2+ and Cd 2+ ions are bioactive, moreover, Zn 2+ ions are biogenic agents [12], and Cd 2+ ions are toxic and carcinogenic [13]. 1,10-Phenanthroline mononuclear Zn 2+ coordination compounds are actively being investigated as potential antibacterial, antifungal and antitumor agents [14]. In recent decades, due to the growing resistance of bacteria, fungi and tumors to the action of antibiotics and traditional drugs based on purely organic substances, interest in metal-medicinal agents has increased [7, 15–16]. Among such agents, mononuclear complexes of d-elements with 1,10-phenanthroline derivatives, as well as 1,10-phenanthroline binuclear bridge structures, occupy an important place [17]. Cd 2+ complexes inhibiting the growth of tumor cells in vitro and in vivo are of interest as active potential drugs in antitumor therapy [10], including neutron capture therapy. One of the ways of antitumor activity of metal complexes with 1,10-phenanthroline is associated with their interaction with DNA macromolecules, their cleavage and inhibition of protein synthesis. The interaction of mononuclear 1,10-phenanthroline Cd(II) compounds with DNA has recently been studied [18]. Previously, we studied the complexation of DNA in an aqueous medium with the acetate 1,10-phenanthroline compound of Zn(II) Zn(phen) 2 (OAc) 2 [19]. DNA intercalation by the action of the complex [Zn(phen) 3 ] 2+ was discovered in [20]. In one of the first publications on the study of the biological activity of perchlorate complexes with 1,10-phenanthroline were characterized: Fe(II) [Ar]3d 6 [Fe(phen) 3 ](ClO 4 ) 2 , Ni(II) [Ar]3d 8 [Ni(phen) 3 ](ClO 4 ) 2 , Ru(II) [Kr]4d 6 [Ru(phen) 3 ](ClO 4 ) 2 [21]. A systematic study of the antibacterial, antiviral, antimycotic and antitumor activity of 1,10-phenanthroline complexes was carried out in a subsequent series of studies [22–27]. They showed a relatively high biostatic effect of these compounds. In recent years, infections caused by antimicrobial-resistant strains have become a global health problem. Resistance of strains such as Enterococcus faecium , Staphylococcus aureus , Klebsiella pneumoniae , Acinetobacter baumanii , P. aeruginosa and Enterobacteriaceae is due to and may further increase due to the intensive use of antibiotics. The development of new antimicrobials is facilitated by knowledge of metal toxicity and the synthesis of metal coordination compounds as effective and targeted antimicrobials in the field of inorganic medicinal chemistry. 1,10-Phenanthroline is a high-field bidentate ligand (the field factor f 1.34 [28]) that forms very stable chelates with many transition metal ions. The N-electron-donating properties (Lewis basicity) of diimine ligands can be estimated on the HEP2 scale of 13 C NMR spectra [29]. In this scale for phen, phen-dione and bpy HEP2 was 161.4, 160.0, and 162.7. That is, N-basicity is maximal for bpy. 1,10-Phenanthroline is also characterized by strong π-acceptor properties [30]. This heterocyclic organic compound also exhibits excellent antimicrobial activity against a wide range of bacterial and fungal pathogens [31]. Cd 2+ ions have antimicrobial properties and are capable of forming metal complexes with N-containing ligands such as 1,10-phenanthroline. Cd 2+ ions behave like a soft Lewis acid, so a ligand such as 1,10-phenanthroline with the character of a soft (intermediate) Lewis base, according to the HSAB ( hard and soft acids and bases ) principle [32], has a high preference for binding Cd 2+ . 1,10-phenanthroline as a ligand is widely used to construct supramolecular architectures. A consequence of the chelating ability of 1,10-phenanthroline is the easy formation of mononuclear metal complexes. These complexes can be used as building blocks for the construction of polymer complexes through weak non-classical C/N-H....X, C/N-H⋯O, C-H.....π hydrogen bonding and π-π stacking interactions. In addition, 1,10-phenanthroline has an extended conjugated planar π electron system and can be used in model compounds to mimic non-covalent interactions in biological processes [33, 34]. Effective Pt(II)-based anticancer chemotherapeutic agents such as cis-platin [Pt(NH 3 ) 2 Cl 2 ] have paved the way for further research to produce new drugs, but with less toxicity and less acquired resistance. Therefore, there is great interest in the development of metal-based drugs that utilize biologically significant elements. The basic principle is that the ion homeostasis of such essential metals will be better regulated by human physiology and cause fewer harmful side effects [35]. As such, Zn 2+ is of great interest, since it is the second most abundant transition metal in the human body after Fe 2+ /Fe 3+ . Zn 2+ ions are known to be present in numerous proteins required for the catalytic activity of more than 200 enzymes [36]. Due to the multiple physiological roles of Zn2 + ions, its complexes have been investigated as DNA-binding compounds, nuclease mimics, insulin mimics, antimicrobials, and as potential anticancer drugs with lower toxicity. The combination of a metal ion with bioactive and/or bioavailable organic ligands is a strategy that may lead to an effective and more selective metal drug [35]. It is generally accepted that Cd 2+ ions, unlike other elements (Zn 2+ , Se 2- and Mg 2+ ), are not necessary for the human body and do not participate in known enzymatic processes. On the other hand, some authors have obtained evidence of cell apoptosis as a result of Cd 2+ intoxication; its ability to cause DNA fragmentation is also known [37–39]. Cd 2+ ions are considered to be quite toxic, but it has been demonstrated that their toxicity depends on the compound used and therefore can be controlled by complexation [40]. In this context Cd(II)-based coordination compounds with N-containing ligands such as 1,10-phenanthroline may be useful for the development of new antimicrobial agents. The activity order is [Cu(bpy)(phen)(H 2 O) 2 ]Cl 2 > [Co(bpy)(phen) 2 ](NO 3 ) 2 > [Zn(bpy) 2 (phen)]Cl 2 [41–43]. 1 H NMR spectra of 1,10-phenanthroline and coordinated 1,10-phenanthroline in diamagnetic d-element complexes have been studied in various publications, covering such aspects as the effect on the position and shape of the signals of the central ion of the complexing agent, as well as solvents. The indication of 1 H NMR spectra in such systems allows one to draw certain conclusions about the structure of compounds. The 1 H NMR spectrum of [Pt(phen)Cl 2 ] is discussed in [44]. In [45], six groups of signals were identified for 1,10-phenanthroline in CDCl 3 in 13 C NMR spectra. For the 1 H NMR spectrum of 1,10-phenanthroline in CDCl 3 (300 MHz), the following sets of signals are given (chemical shift values δ ppm, relative intensity is given in parentheses): 7.56 (231), 7.57 (237), 7.59 (254), 7.60 (257); 8.18 (263), 8.19 (267), 8.21 (258), 8.22 (1000); 9.17 ((258), 9.18 (259), 9.19 (250) [46]. In [47] the following assignments were made for the signals of 1,10-phenanthroline in 1 H and 13 C NMR spectra: δ H (300.1 MHz, CDCl 3 ) 9.18 (dd, J 4.2,1.8, 2H, H2 + H9), 8.23 (dd, J 8.1, 1.5, 2H, H4 + H7), 7.77 (s, 2H, H5 + H6), 7.62 (dd, J 7.8, 4.3, 2H, H3 + H8). δ C (75 MHz, CDCl 3 ) 123.1 (C3 + C8), 126.6 (C5 + C6), 128.7 (C13 + C14), 136.0 (C4 + C7), 146.3 (C11 + C12), 150.4 (C2 + C9). Detailed analysis of 1 H and 13 C NMR spectra 1,10-phenanthroline was carried out in [48]. For 1,10-phen•H 2 O and [Mg(phen) 3 ](NO 3 ) 2 •9H 2 O in DMSO-D 6 the following values of δ H (ppm): 2,9- 9.12 (d), 4,7- 8.52 (d), 5,6- 8.02 (s), 3,8- 7.80 (q); 2,9- 8.95, 4,7- 8.88, 5,6- 8.33 (s), 3,8–8.00 (q) were found [49]. In this work, the 1 H and 13 C NMR spectra of mixed-ligand acetate complexes of Zn(II) and Cd(II) with 1,10-phenanthroline were systematically studied for the first time. 2 Experimental Part 2.1 Materials and Methods 2.1.1 Starting Materials 1,10-Phenanthroline monohydrate phen·H 2 O (clean for analysis, production in Germany) was purchased in LenReactiv (192240, St. Petersburg, Russia, 6th Preport passage, 8), zinc acetate dihydrate Zn(AcO) 2 •2H 2 O (chemically pure, production in Russia), cadmium acetate dihydrate Cd(AcO) 2 •2H 2 O (chemically pure, production in Russia) — in NevaReactiv (195043, St. Petersburg, Russia, Kapsulnoe highway, 45). 2.2 Synthesis of Zn 2+ and Cd 2+ mononuclear 1,10-phenanthroline acetate complexes The synthesis of mononuclear 1,10-phenanthroline complexes of Zn 2+ and Cd 2+ M(phen) n (OAc) 2 • 2H 2 O (M = Zn 2+ and Cd 2+ , n = 1–3) was carried out by complexation of M(OAc) 2 •2H 2 O acetates with 1,10-phenanthroline monohydrate in aqueous solutions at a temperature of 90–95 ° C (n = 1), or in melts at a temperature of 110–115 ° C (n = 2, 3), heating mixtures of starting substances for about 1 hour in stoichiometric ratios. According to the data of the elemental analysis, the composition of the compounds corresponds to the formulas given (Fig. 1 , 1 – 3 , a M = Zn 2+ , b M = Cd 2+ ). The IR spectra of substances (in tablets with KBr, 2000 − 400 cm -1 ) indicate the coordination of 1,10-phenanthroline to Zn 2+ and Cd 2+ ions, respectively. The compounds are highly soluble in water at room temperature. The resulting solutions are colorless. Synthesis of diacetato-mono(1,10-phenanthroline)zinc dihydrate Zn(phen)(OAc) 2 • 2H 2 O A stoichiometric equimolar amount (1 mol: 1 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was gradually added to a concentrated aqueous solution of zinc acetate dihydrate Zn(OAc) 2 •2H 2 O at a temperature of 90–95 o C and stirring. This forms a colorless solution. Then heating was continued for about 1 hour. With partial evaporation of water, the colorless complex Zn(phen)(OAc) 2 •2H 2 O crystallized. It was separated and dried at room temperature. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 44.7, H 4.4, N 7.2. For Zn(phen)(OAc) 2 •2H 2 O, C 14 H 18 N 2 O 6 Zn, calculated, %: C 44.92, H 4.81, N 7.49. Synthesis of diacetato-bis(1,10-phenanthroline)zinc dihydrate Zn(phen) 2 (OAc) 2 •2H 2 O A mixture of solid zinc acetate dihydrate Zn(OAc) 2 •2H 2 O and a stoichiometric amount (1 mol: 2 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was thermostated at a temperature of 110–115 o C for about 1 hour. A colorless glassy compound Zn(phen) 2 (OAc) 2 •2H 2 O is formed. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 44.7, H 4.4, N 7.2. For Zn(phen) 2 (OAc) 2 •2H 2 O, C 26 H 26 N 4 O 6 Zn, calculated, %: C 44.92, H 4.81, N 7.49. Synthesis of tris(1,10-phenanthroline)zinc(II) acetate dihydrate [Zn(phen) 3 ](OAc) 2 • 2H 2 O A mixture of solid zinc acetate dihydrate Zn(OAc) 2 •2H 2 O and a stoichiometric amount (1 mol: 3 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was thermostated at a temperature of 110–115 o C for about 1 hour. A colorless glassy compound [Zn(phen) 3 ](OAc) 2 •2H 2 O is formed. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 62.0, H 4.4, N 11.2. For [Zn(phen) 3 ](OAc) 2 •2H 2 O, C 38 H 34 N 6 O 6 Zn, calculated, %: C 62.12, H 4.63, N 11.44. Synthesis of diacetato-mono(1,10-phenanthroline)cadmium dihydrate Cd(phen)(OAc) 2 • 2H 2 O A stoichiometric amount (1 mol: 1 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was gradually added to a concentrated aqueous solution of cadmium acetate dihydrate Cd(OAc) 2 •2H 2 O at a temperature of 90–95 o C and stirring. This forms a colorless solution. Heating was then continued for about 1 hour. Upon partial evaporation of water, the colorless complex Cd(phen)(OAc) 2 •2H 2 O crystallizes. It was separated and dried at room temperature. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 39.4, H 4.1, N 6.4. For Cd(phen)(OAc) 2 •2H 2 O, C 14 H 18 N 2 O 6 Cd, calculated, %: C 39.62, H 4.25, N 6.60. Synthesis of diacetato-bis(1,10-phenanthroline)cadmium dihydrate Cd(phen) 2 (OAc) 2 •2H 2 O A mixture of solid cadmium acetate dihydrate Cd(OAc) 2 •2H 2 O and a stoichiometric amount (1 mol: 2 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was thermostated at a temperature of 110–115 o C for about 1 hour. A colorless glassy compound Cd(phen) 2 (OAc) 2 •2H 2 O is formed. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 51.4, H 4.3, N 9.2. For Cd(phen) 2 (OAc) 2 •2H 2 O, C 26 H 26 N 4 O 6 Cd, calculated, %: C 51.65, H 4.30, N 9.27. Synthesis of tris(1,10-phenanthroline)cadmium(II) acetate dihydrate [Cd(phen) 3 ] (OAc) 2 •2H 2 O A mixture of solid cadmium acetate dihydrate Cd(OAc) 2 •2H 2 O and a stoichiometric amount (1 mol: 3 mol) of 1,10-phenanthroline monohydrate phen•H 2 O was thermostated at a temperature of 110–115 o C for about 1 hour. A colorless glassy compound [Cd(phen) 3 ](OAc) 2 •2H 2 O is formed. The compound is highly soluble in water and soluble in DMSO. Elemental analysis–found, %: С 62.0, H 4.4, N 11.2. For [Cd(phen) 3 ](OAc) 2 •2H 2 O, C 38 H 34 N 6 O 6 Cd, calculated, %: C 62.12, H 4.63, N 11.44. 2.3 NMR Measurements Measurements of the NMR spectra of Zn 2+ and Cd 2+ complexes were carried out on the NMR spectrometer Bruker 500 MHz Avance III at the Magnetic Resonance Methods of Investigation Resource Center (MRMI RC) of the St. Petersburg Science Park of St. Petersburg State University, and also at the Bioengineering Center of St. Petersburg State Technological Institute (Technical University) on the NMR spectrometer Bruker BioSpin AG, Avance III HD 400 MHz. 3 Results and Discussion The production of glassy nanoscale polymorphic binuclear chromophore 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) Zn 2+ and Cd 2+ with pharmacophore bridging ligands (phen) n M(µ-N-biphen)M(phen) n (OAc) 4 (n = 0–2) was carried out using the original methodology of metal-assisted non-dehydrogenative C(sp 2 ) H coupling coordinated 1,10-phenanthroline in acetate complexes of d-elements [7–9]. The synthesis of binuclear chromophore 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) Zn 2+ and Cd 2+ was carried out in melts at a temperature of 200–205°C, heating the corresponding simple mononuclear 1,10-phenanthroline precursors for 25–30 minutes. As a result of the C(sp 2 ) H coupling of coordinated 1,10-phenanthroline, after cooling the black-purple melts, the compounds were obtained in a glassy state. 1,10-Phenanthrocyanines (bi-1,10-phenanthrolylenes) are highly soluble in chloroform, DMF and DMSO at room temperature with the formation of intensely colored purple-violet solutions. IR spectra of substances (in tablets with KBr, 2000 − 400 cm -1 ) confirm the coordination of 1,10-phenanthroline to Zn 2+ and Cd 2+ ions, respectively. For example, Fig. 1 shows the structure of M(µ-N-biphen)M(OAc) 4 , M 2+ = Zn 2+ , Cd 2+ . The 1 H and 13 C NMR spectra of glassy binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes or N-heterophenylenes) of Zn 2+ and Cd 2+ show signal sets of a significantly more complex structure than mononuclear acetate 1,10-phenanthroline precursors corresponding to both 1,10-phenanthroline ligands and bridged 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes). The latter contain dihydro -bi-1,10-phenanthroline fragments, which appear in the 1 H NMR spectra in the range 5.0-7.5 ppm. The detection of signals belonging to the bridge chromophores of µ-biphen was performed on the basis of NMR spectra of Zn 2+ and Cd 2+ (Fig. 2) compounds that do not contain pure 1,10-phenanthroline ligands. The study of 1 H and 13 C NMR spectra of glassy binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes or N-heterophenylenes) of Zn 2+ and Cd 2+ in DMSO-D 6 solutions shows that, compared with their simple mononuclear precursors, binuclear chromophore complexes contain bridging ligands of a significantly more complex nature than 1,10-phenanthroline. These are electron-rich pharmacophore 1,10-phenanthrocyanine C–C-dimers. These bridging ligands modify the biocidal action of mononuclear 1,10-phenanthroline precursors. The studied binuclear compounds can be used as modulators of microbial activity, in particular, as «soft» biostatic antifouling agents. 3.1 Investigation of Zn 2+ and Cd 2+ mononuclear 1,10-phenanthroline acetate complexes by NMR Specrtoscopy The 1 H and 13 C NMR spectra of solutions in D 2 O and deuterated organic solvent DMSO-D 6 of mononuclear Zn 2+ and Cd 2+ 1,10-phenanthroline complexes: M(phen) n (OAc) 2 • 2H 2 O (M = Zn 2+ and Cd 2+ , n = 1–3, 1–3 a , b ) (Fig. 3 ) of binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) (phen) n M(µ-biphen)M(phen) n (OAc) 4 (n = 0–2) with pharmacophore bridging ligands were studied. The 1 H and 13 C NMR spectra of simple mononuclear 1,10-phenanthroline acetates of Zn 2+ 1–3 and Cd 2+ 1a-3b in D 2 O and DMSO-D 6 contain a set of signals characteristic of coordinated 1,10-phenanthroline. The coordination of 1,10-phenanthroline to Zn 2+ and Cd 2+ ions has almost no effect on the chemical shifts of the signals of hydrogen atoms in the heteroaromatic region. While the nature of the solvent significantly affects them. And during the transition from D 2 O to DMSO-D 6 , the proton signals of the heteroaromatic ring shift to a low field. The largest shifts in proton signals were detected for the binary solvent D 2 O–DMSO-D 6 (1:1). The 1 H and 13 C NMR spectra of solutions in D 2 O and deuterated organic solvent DMSO-D 6 of mononuclear Zn 2+ and Cd 2+ 1,10-phenanthroline complexes: M(phen) n (OAc) 2 • 2H 2 O (M = Zn 2+ и Cd 2+ , n = 1–3, 1–3 a , b ) (Fig. 3 ) of binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) (phen) n M(µ-biphen)M(phen) n (OAc) 4 (n = 0–2) with pharmacophore bridging ligands were studied. Shift in the low field of heteroaromatic proton signals in 1.10-phenanthroline ring in 1 H NMR spectra of complexes in the sequence: 3,8- < 5,6- < 4,7- < 2,9 ( 4–8, 10, 12, Table 1 , Scheme 1) is consistent with an increase in the electron acceptor effect of N atoms in 1,10-phenanthroline ring, which it is implemented in the same sequence. The 1 H and 13 C NMR spectra of simple mononuclear 1,10-phenanthroline acetates of Zn 2+ 1a - 3a and Cd 2+ 1b - 3b in D 2 O and DMSO-D 6 contain a set of signals characteristic of coordinated 1,10-phenanthroline (Tables 1 , 2 ). The coordination of 1,10-phenanthroline to Zn 2+ and Cd 2+ ions has almost no effect on the chemical shifts of the signals of hydrogen atoms in the heteroaromatic region. While the nature of the solvent significantly affects them. And during the transition from D 2 O to DMSO-D 6 for coordination-unsaturated complexes 1a , 2a , 1b and 2b the proton signals of the heteroaromatic ring shift to a low field. The largest shifts in proton signals were detected for the binary solvent D 2 O–DMSO-D 6 (1:1). When analyzing the 1 H and 13 C NMR spectra of compounds, attention should be paid to the fact that the NMR parameters of acetate groups (Table 3 ) are close for complexes and simple salts (Fig. 13 , 14). This should indicate that the acetate groups in the solutions of the complexes are in all cases external. That is, dissociation and solvation reactions (S – solvent, D 2 O or DMSO-D 6 ) occur rapidly in solutions of complexes: M(phen) n (OAc) 2 → M(phen) n 2+ + 2 OAc − (M = Zn 2+ , Cd 2+ , n = 1, 2) M(phen) 2+ + 4 S→ [M(phen)S 4 ] 2+ M(phen) 2 2+ + 2 S→ [M(phen) 2 S 2 ] 2+ [M(phen) 3 ](OAc) 2 → [M(phen) 3 ] 2+ + 2 OAc − (M = Zn 2+ , Cd 2+ ) The coordination of DMSO-D 6 to Zn + 2 and Cd 2+ ions, as soft Lewis acids, should be carried out through its soft donor atom S in accordance with the principle of hard and soft acids and bases (HSAB) [32] Unexpected was the fact that in the case of the M(phen) n (OAc) 2 •2H 2 O complexes (M = Zn + 2 and Cd 2+ , n = 1,2), the effect on the chemical shifts of the δ H protons in the heteroaromatic region of the 1 H NMR spectra for the DMSO-D 6 –D 2 O (1:1) mixture was maximal, which is unprecedented. For D 2 O–DMSO-D 6 mixture, there is a strong shift of δ H values to a low field (Table 1 ). This is most likely due to the formation of solvates in solutions containing both D 2 O (S1) and DMSO-D 6 (S2): M(phen) 2+ + 2 S1 + 2 S2 → [M(phen)S1 2 S2 2 ] 2+ M(phen) 2 2+ + S1 + S2→ [M(phen) 2 S1S2] 2+ For 13 C signals such an offset in D 2 O–DMSO-D 6 mixture is not observed (Table 2 ). 4 Conclusions It was found that the chemical shifts of the δ H protons of the heteroaromatic rings of 1,10-phenanthroline are sensitive to coordination with Zn + 2 and Cd 2+ ions, but the type of solvent has the greatest effect on δ H . For M(phen) n (OAc) 2 •2H 2 O (М = Zn + 2 and Cd 2 , n = 1, 2) complexes, the maximum shift to a weak field of δ H values occurs for the mixed solvent D 2 O–DMSO-D 6 . For complexes [M(phen) 3 ](OAc) 2 •2H 2 O in the solvent D 2 O–DMSO-D 6 , on the contrary, there is a very weak shift of the values of δ H in a strong field compared with the values for DMSO-D 6 and in a weak field compared with the values in D 2 O. The difference in the 1 H NMR spectral pattern for compounds M(phen) n (OAc) 2 •2H 2 O (n = 1,2) and [M(phen) 3 ](OAc) 2 •2H 2 O should be associated with the coordination saturation of the latter, for which the insertion of a solvent – D 2 O or DMSO-D 6 into the internal coordination sphere is practically impossible While the complexes M(phen) n (OAc) 2 •2H 2 O (n = 1, 2) are coordination-unsaturated structures and allow solvent molecules to penetrate into their internal coordination sphere by substitution of acetate groups − OAc. It is unexpected that in the case of M(phen)n(OAc) 2 •2H 2 O complexes (M = Zn + 2 and Cd 2+ , n = 1, 2), the effect on the chemical shifts of δ H protons in the heteroaromatic region of the 1 H NMR spectra for D 2 O–DMSO-D 6 (1 : 1) mixture is maximal, which is unprecedented. Declarations Author Contributions VND wrote a manuscript, synthesized compounds, participated in the formulation of the concept (while performing the main role), AGI participated in the formulation of the concept, INT, VIV, YAK, IBG, TBP participated in the synthesis of compounds, their characterization and depicted structural formulas. All authors have reviewed the manuscript. Funding The work was carried out at I.V. Grebenschikov Institute of Silicate Chemistry of the Russian Academy of Sciences within the framework of the theme of the state budget: “Physical-chemical bases of inorganic synthesis of micro- and nanostructured non-organic, organo-non-organic and ceramic materials and coatings for bio-, energy- and resource-saving technologies.” (1023033000122-7-1.4.3). Availability of Data and Materials The materials are available in the databases of I.V. Grebenschikov Institute of the Silicate Chemistry of the Russian Academy of Sciences and the Resource Center “Magnetic Resonance Research Methods” of St. Petersburg State University, and also at the Bioengineering Center of St. Petersburg State Technological Institute (Technical University). Confict of interest The authors declare that they have no competing interests. Ethical approval Not applicable. References V.N. Demidov, V.G. Puzenko, A.I. Savinova, N.S. Panina, T.B. Pakhomova, L.N. Vedeneeva, S.A. Simanova, Electron-rich metal phenanthrocyanine - new class of tetraazachromophore complexes of d-elements. News MIFCT, Fine Chem. Technol. 2 (3), 36-43 (2007). ( in Russian ) V.N. Demidov, Electron-rich 1,10-phenanthrocyanine complexes of d-elements: patterns of formation, spectral properties, structural and thermodynamic similarity -Diss. Doct. Chem. Sci., St. Petersburg State Technol. Inst. (Techn. Univ.), St. Petersburg, 2010, 450 p. ( in Russian ) V.N. Demidov, S.A. Simanova, A.I. 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Atanassova, Synthesis and spectroscopic characterization of a complex of 1,10-phenanthroline with magnesium. Z. Anorg. Allg. Chem. 629 (1), 12-14 (2003). https://doi.org/10.1002/zaac.200390005 Tables Table 1 1,10-phenanthroline ring parameters of 1 H NMR spectra of Zn(II) and Cd(II) complexes with 1,10-phenanthroline No. of comp. Compound Solvent The chemical shifts of H atoms in 1,10-phenanthroline ring, δ H (ppm) The position of the H atoms in the cycle of 1,10-phenanthroline (Scheme 1) 3,8- 5,6- 4,7- 2,9- 1a 2a 1b 3b 4 Zn(phen)(OAc) 2 •2H 2 O Zn(phen) 2 (OAc) 2 •2H 2 O Cd(phen)(OAc) 2 •2H 2 O [Cd(phen) 3 ](OAc) 2 •2H 2 O 1,10-phen•H 2 O D 2 O DMSO-D 6 DMSO-D 6 D 2 O– DMSO-D 6 * D 2 O DMSO-D 6 D 2 O– DMSO-D 6 * D 2 O DMSO-D 6 D 2 O– DMSO-D 6 * DMSO-D 6 7.36 8.07 7.94 9.97 7.21 7.99 10.07 7.46 7.86, 7.87 7.75 7.72 7.63, 7.88 8.21 8.12 10.09 7.54 8.16 10.18 7.52, 7.54 8.05 7.88 7.94 8.13, 8.34 8.85 8.72 10.29 7.99 8.74, 8.76 10.78 8.17, 8.19 8.54, 8.61 8.50, 8.52 8.44 8.47, 8.74 9.06 9.03 10.90 8.60 9.06 11.08 8.39 8.91 8.65 9.09 *) in mixture D 2 O–DMSO-D 6 (1:1) Table 2 1,10-phenanthroline ring parameters of 13 C NMR spectra of Zn(II) and Cd(II) complexes with 1,10-phenanthroline and 1,10-phenanthroline monohydrate No. of comp. Compound Solvent The chemical shifts of C atom in 1,10-phenanthroline ring, δ C (ppm) The position of the C atoms in the cycle of 1,10-phenanthroline (Scheme 1) 3,8- 5,6- 13,14- 4,7- 11,12- 2,9- 1a 2a 1b 3b 4 Zn(phen)(OAc) 2 •2H 2 O Zn(phen) 2 (OAc) 2 •2H 2 O Cd(phen)(OAc) 2 •2H 2 O [Cd(phen) 3 ](OAc) 2 •2H 2 O phen•H 2 O D 2 O DMSO-D 6 DMSO-D 6 D 2 O–DMSO- D 6 * D 2 O DMSO-D 6 D 2 O–DMSO- D 6 * D 2 O DMSO-d 6 D 2 O–DMSO- D 6 * DMSO-D 6 125.16 126.09 125.23 128.07 124.84 125.38 124.97 125.66 125.55 123.68 126.32 127.43 127.34 129.56 126.43 127.41 129.59 127.06 126.91 127.58 127.11 128.25 128.87 128.88 128.49 128.87 131.31 129.33 129.56 128.89 140.18 138.67 142.65 139.39 139.11 141.97 139.97 139.79 140.19 136.55 139.79 140.64 142.62 150.83 149.35 141.07 140.45 139.79 140.86 145.89 148.48 150.09 150.04 150.83 149.35 150.49 152.23 149.39 149.12 149.99 150.39 *) in mixture D 2 O–DMSO-D 6 (1:1) Table 3 Acetate groups parameters of 1 H and 13 C NMR spectra of Zn(II) and Cd(II) acetate complexes with 1,10-phenanthroline and Cd(OAc) 2 •2H 2 O No. of comp. Compound Solvent The chemical shifts of H atoms in CH 3 –groups of CH 3 CO 2 – anions, δ H (ppm) The chemical shifts of C atoms in CH 3 –groups of CH 3 CO 2 – anions, δ C (ppm) The chemical shifts of C atoms in CO 2 –groups of CH 3 CO 2 – anions, δ C (ppm) 1a 2a 1b 3b 6 Zn(phen)(OAc) 2 •2H 2 O Zn(phen) 2 (OAc) 2 •2H 2 O Cd(phen)(OAc) 2 •2H 2 O [Cd(phen) 3 ](OAc) 2 •2H 2 O Cd(OAc) 2 •2H 2 O D 2 O DMSO-D 6 DMSO-D 6 D 2 O– DMSO-D 6 * D 2 O DMSO-D 6 D 2 O– DMSO-D 6 * D 2 O DMSO-D 6 D 2 O– DMSO-D 6 * D 2 O D 2 O– DMSO-D 6 * 1.76 (1.59, 1.92) 1.79 (1.63, 1.94) 3.44 1.76 (1.61, 1.92) 2.50 4.72, 3.91 1.81 1.77 (1.61, 1.92) 2.50 (2.32, 2.68) 4.01 (3.85, 4.17) 4.72 1.71 1.77 (1.59, 1.92) 1.74 1.79 (1.63, 1.94) 4.76 4.05 (4.02, 4.16) 4.72 22.62 23.08 23.32 25.87 22.05 22.85 24.83 23.06 23.13 23.09 21.82 24.36 181.58 177.89 177.69 181.80 181.36 176.81 181.57 181.14 179.84 178.34 181.62 185.54 *) in mixture D 2 O–DMSO-D 6 (1:1) Schemes Scheme 1 is available in the Supplementary Files section Additional Declarations No competing interests reported. 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1","display":"","copyAsset":false,"role":"figure","size":17481,"visible":true,"origin":"","legend":"\u003cp\u003eCoordination environment of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e in 1,10-phenanthrocyanine \u003cstrong\u003eM(µ-N-biphen)M(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/ba3e753ff34ef103f3055ce2.png"},{"id":59263583,"identity":"b9445859-f4e3-46e9-8eb5-66d3d5b9e577","added_by":"auto","created_at":"2024-06-28 10:27:44","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":54127,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectrum of complex \u003cstrong\u003eCd(µ-N-biphen)Cd(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e (purple form) in DMSO-d\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/24b8eabdac5a794881f6daf1.png"},{"id":59263584,"identity":"ce30dbd0-0b03-4c4e-a2eb-1aba1bde25ab","added_by":"auto","created_at":"2024-06-28 10:27:44","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":8578,"visible":true,"origin":"","legend":"\u003cp\u003eCoordination environment of Zn\u003csup\u003e2+ \u003c/sup\u003eand Cd\u003csup\u003e2+\u003c/sup\u003e in 1,10-phenanthroline complexes \u003cstrong\u003e1 (a\u003c/strong\u003e,\u003cstrong\u003e b)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/25cf1aaa387403495d90b906.png"},{"id":59263215,"identity":"4a75b417-9e24-4b57-a95e-64c14a1879a9","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":4,"title":"Figure 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\u003cstrong\u003e1a \u003c/strong\u003ein DMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/0b2a96684546edc6b0c036d7.png"},{"id":59263226,"identity":"63e79e69-2c65-45d7-8caf-7c3556cd7e3c","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":66940,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of complex Cd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO \u003cstrong\u003e1b\u003c/strong\u003e in D\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/bf26a30b3264cb5f58ce11ec.png"},{"id":59263217,"identity":"662738d8-2528-4c67-a50c-74b0509439d2","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":70770,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of complex Cd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO \u003cstrong\u003e1b\u003c/strong\u003e in DMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/fe1ac0656cdab79e8ec6a96b.png"},{"id":59263221,"identity":"7089c8a7-baa4-4363-84ec-ca8423994434","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":66951,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of complex Cd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO \u003cstrong\u003e1b\u003c/strong\u003e in D\u003csub\u003e2\u003c/sub\u003eO–DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1)\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/90a365cf4965ce5f26fd1075.png"},{"id":59263588,"identity":"d430393e-a6be-486c-8eb0-1fe1777fc7a8","added_by":"auto","created_at":"2024-06-28 10:27:44","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":12916,"visible":true,"origin":"","legend":"\u003cp\u003eCoordination environment of Zn\u003csup\u003e2+ \u003c/sup\u003eand Cd\u003csup\u003e2+\u003c/sup\u003e in 1,10-phenanthroline complexes \u003cstrong\u003e2 (a\u003c/strong\u003e,\u003cstrong\u003e b)\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/acf1b1e66c3f66d8be57e229.png"},{"id":59263228,"identity":"a46b1b20-56d9-4393-b50c-dd114d9fb3cd","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":54211,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of complex Zn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO \u003cstrong\u003e2a\u003c/strong\u003e in 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12","display":"","copyAsset":false,"role":"figure","size":42994,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of phen•H\u003csub\u003e2\u003c/sub\u003eO in DMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/39bf9710d5ae16144f83cfa4.png"},{"id":59263224,"identity":"381715d3-5492-429c-b694-7f2e17073918","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":32749,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of Cd(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO in D\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/ae9afffea2319859c0a1e906.png"},{"id":59263220,"identity":"9cbfa76d-c865-4f2d-a2e3-aa5e24d03a20","added_by":"auto","created_at":"2024-06-28 10:19:44","extension":"png","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":52162,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH (a) and \u003csup\u003e13\u003c/sup\u003eC (b) NMR spectra of Cd(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO in D\u003csub\u003e2\u003c/sub\u003eO–DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1)\u003c/p\u003e","description":"","filename":"14.png","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/cf0c1402ce4a95d9d912431d.png"},{"id":59264375,"identity":"9a345e91-e506-40e7-b48b-43d700115d5c","added_by":"auto","created_at":"2024-06-28 10:43:46","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1814873,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/85373136-670d-4b59-b1f0-79d6eb792d20.pdf"},{"id":59263582,"identity":"e2c5a800-1358-4311-8b8e-4498cd3b1098","added_by":"auto","created_at":"2024-06-28 10:27:44","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":37955,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-4553203/v1/c3f2903a161c7e3658d4b1cf.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eEffect of the coordination centers and the solvents on the parameters of the \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of biology active Zn\u003csup\u003e+2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e acetate mononuclear complexes with chelating 1,10- phenanthroline\u003c/p\u003e","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eAcetate 1,10-phenanthroline complexes are the precursors of the compounds of the new apo-1,10-phenanthrocyanine class systematically studied by us: metallo-N-heterobiphenylenes \u0026ndash; glassy \u003cem\u003eelectron-rich\u003c/em\u003e binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) \u003cb\u003eL\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e(phen)\u003c/b\u003e\u003csub\u003e\u003cb\u003em\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eM(\u0026micro;-N-biphen)M(phen)\u003c/b\u003e\u003csub\u003e\u003cb\u003em\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eL\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(OAc)\u003c/b\u003e\u003csub\u003e\u003cb\u003el\u003c/b\u003e\u003c/sub\u003e of d-elements (\u003cb\u003eM\u003c/b\u003e) \u003cb\u003eZn\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e [Ar]3d\u003csup\u003e10\u003c/sup\u003e, \u003cb\u003eCd\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e [Kr]4d\u003csup\u003e10\u003c/sup\u003e, \u003cb\u003eCo\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e [Ar]3d\u003csup\u003e7\u003c/sup\u003e, \u003cb\u003eMn\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e [Ar]3d\u003csup\u003e5\u003c/sup\u003e, \u003cb\u003eNi\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e [Ar]3d\u003csup\u003e8\u003c/sup\u003e, \u003cb\u003eCr\u003c/b\u003e\u003csup\u003e\u003cb\u003e3+\u003c/b\u003e\u003c/sup\u003e [Ar]3d\u003csup\u003e3\u003c/sup\u003e (phen\u0026thinsp;=\u0026thinsp;1,10-phenanthroline, L \u0026ndash; amine ligands, OAc\u003csup\u003e-\u003c/sup\u003e \u0026ndash; acetate groups) [1\u0026ndash;3]. In their structure, compounds of the new class contain bridging chromophores \u0026ndash; pharmacophore ligands of \u003cb\u003e\u0026micro;-N-biphen\u003c/b\u003e, which are characterized by the presence of \u003cem\u003etemperature-accessible lowest electronic biradical triplet states\u003c/em\u003e T\u003csub\u003elow\u003c/sub\u003e. [4\u0026ndash;6]. We have established that mononuclear 1,10-phenanthroline acetates of Zn\u003csup\u003e2+\u003c/sup\u003e, Cd\u003csup\u003e2+\u003c/sup\u003e, Co\u003csup\u003e2+\u003c/sup\u003e and Mn\u003csup\u003e2+\u003c/sup\u003e exhibit strong biocidal properties. They effectively inhibit some micromycete fungi. In this work, the NMR spectra of \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC mononuclear 1,10-phenanthroline acetate compounds of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e were studied in order to use the data obtained to analyze similar spectra of binuclear complexes of a new class \u0026ndash; N-heterobiphenylenes.\u003c/p\u003e \u003cp\u003eMononuclear coordination compounds of Zn\u003csup\u003e2+\u003c/sup\u003e with 1,10-phenanthrolines have recently been investigated as potential antibacterial, antifungal and antitumor agents [7]. Interest in metallo-medicinal agents is increasing due to the growing resistance of bacteria, fungi and tumors to the action of antibiotics and traditional drugs [8, 9]. Mononuclear complexes of d-elements with 1,10-phenanthroline derivatives occupy an important place among such agents [10]. Cd\u003csup\u003e2+\u003c/sup\u003e complexes inhibiting the growth of tumor cells are of interest as active potential drugs in antitumor therapy [11].\u003c/p\u003e \u003cp\u003eIt is known that many metal ions play a very important role in the biological processes of many living organisms. Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions are bioactive, moreover, Zn\u003csup\u003e2+\u003c/sup\u003e ions are biogenic agents [12], and Cd\u003csup\u003e2+\u003c/sup\u003e ions are toxic and carcinogenic [13]. 1,10-Phenanthroline mononuclear Zn\u003csup\u003e2+\u003c/sup\u003e coordination compounds are actively being investigated as potential antibacterial, antifungal and antitumor agents [14]. In recent decades, due to the growing resistance of bacteria, fungi and tumors to the action of antibiotics and traditional drugs based on purely organic substances, interest in metal-medicinal agents has increased [7, 15\u0026ndash;16]. Among such agents, mononuclear complexes of d-elements with 1,10-phenanthroline derivatives, as well as 1,10-phenanthroline binuclear bridge structures, occupy an important place [17]. Cd\u003csup\u003e2+\u003c/sup\u003e complexes inhibiting the growth of tumor cells \u003cem\u003ein vitro\u003c/em\u003e and \u003cem\u003ein vivo\u003c/em\u003e are of interest as active potential drugs in antitumor therapy [10], including neutron capture therapy.\u003c/p\u003e \u003cp\u003eOne of the ways of antitumor activity of metal complexes with 1,10-phenanthroline is associated with their interaction with DNA macromolecules, their cleavage and inhibition of protein synthesis. The interaction of mononuclear 1,10-phenanthroline Cd(II) compounds with DNA has recently been studied [18]. Previously, we studied the complexation of DNA in an aqueous medium with the acetate 1,10-phenanthroline compound of Zn(II) Zn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e [19]. DNA intercalation by the action of the complex [Zn(phen)\u003csub\u003e3\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e was discovered in [20]. In one of the first publications on the study of the biological activity of perchlorate complexes with 1,10-phenanthroline were characterized: Fe(II) [Ar]3d\u003csup\u003e6\u003c/sup\u003e [Fe(phen)\u003csub\u003e3\u003c/sub\u003e](ClO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e, Ni(II) [Ar]3d\u003csup\u003e8\u003c/sup\u003e [Ni(phen)\u003csub\u003e3\u003c/sub\u003e](ClO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e, Ru(II) [Kr]4d\u003csup\u003e6\u003c/sup\u003e [Ru(phen)\u003csub\u003e3\u003c/sub\u003e](ClO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e [21]. A systematic study of the antibacterial, antiviral, antimycotic and antitumor activity of 1,10-phenanthroline complexes was carried out in a subsequent series of studies [22\u0026ndash;27]. They showed a relatively high biostatic effect of these compounds.\u003c/p\u003e \u003cp\u003eIn recent years, infections caused by antimicrobial-resistant strains have become a global health problem. Resistance of strains such as \u003cem\u003eEnterococcus faecium\u003c/em\u003e, \u003cem\u003eStaphylococcus aureus\u003c/em\u003e, \u003cem\u003eKlebsiella pneumoniae\u003c/em\u003e, \u003cem\u003eAcinetobacter baumanii\u003c/em\u003e, \u003cem\u003eP. aeruginosa\u003c/em\u003e and \u003cem\u003eEnterobacteriaceae\u003c/em\u003e is due to and may further increase due to the intensive use of antibiotics. The development of new antimicrobials is facilitated by knowledge of metal toxicity and the synthesis of metal coordination compounds as effective and targeted antimicrobials in the field of inorganic medicinal chemistry.\u003c/p\u003e \u003cp\u003e1,10-Phenanthroline is a high-field bidentate ligand (the field factor \u003cem\u003ef\u003c/em\u003e 1.34 [28]) that forms very stable chelates with many transition metal ions. The N-electron-donating properties (Lewis basicity) of diimine ligands can be estimated on the HEP2 scale of \u003csup\u003e13\u003c/sup\u003eC NMR spectra [29]. In this scale for phen, phen-dione and bpy HEP2 was 161.4, 160.0, and 162.7. That is, N-basicity is maximal for bpy. 1,10-Phenanthroline is also characterized by strong π-acceptor properties [30].\u003c/p\u003e \u003cp\u003eThis heterocyclic organic compound also exhibits excellent antimicrobial activity against a wide range of bacterial and fungal pathogens [31]. Cd\u003csup\u003e2+\u003c/sup\u003e ions have antimicrobial properties and are capable of forming metal complexes with N-containing ligands such as 1,10-phenanthroline. Cd\u003csup\u003e2+\u003c/sup\u003e ions behave like a soft Lewis acid, so a ligand such as 1,10-phenanthroline with the character of a soft (intermediate) Lewis base, according to the HSAB (\u003cem\u003ehard and soft acids and bases\u003c/em\u003e) principle [32], has a high preference for binding Cd\u003csup\u003e2+\u003c/sup\u003e. 1,10-phenanthroline as a ligand is widely used to construct supramolecular architectures. A consequence of the chelating ability of 1,10-phenanthroline is the easy formation of mononuclear metal complexes. These complexes can be used as building blocks for the construction of polymer complexes through weak non-classical C/N-H....X, C/N-H⋯O, C-H.....π hydrogen bonding and π-π stacking interactions. In addition, 1,10-phenanthroline has an extended conjugated planar π electron system and can be used in model compounds to mimic non-covalent interactions in biological processes [33, 34].\u003c/p\u003e \u003cp\u003eEffective Pt(II)-based anticancer chemotherapeutic agents such as cis-platin [Pt(NH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e] have paved the way for further research to produce new drugs, but with less toxicity and less acquired resistance. Therefore, there is great interest in the development of metal-based drugs that utilize biologically significant elements. The basic principle is that the ion homeostasis of such essential metals will be better regulated by human physiology and cause fewer harmful side effects [35].\u003c/p\u003e \u003cp\u003eAs such, Zn\u003csup\u003e2+\u003c/sup\u003e is of great interest, since it is the second most abundant transition metal in the human body after Fe\u003csup\u003e2+\u003c/sup\u003e/Fe\u003csup\u003e3+\u003c/sup\u003e. Zn\u003csup\u003e2+\u003c/sup\u003e ions are known to be present in numerous proteins required for the catalytic activity of more than 200 enzymes [36]. Due to the multiple physiological roles of Zn2\u0026thinsp;+\u0026thinsp;ions, its complexes have been investigated as DNA-binding compounds, nuclease mimics, insulin mimics, antimicrobials, and as potential anticancer drugs with lower toxicity. The combination of a metal ion with bioactive and/or bioavailable organic ligands is a strategy that may lead to an effective and more selective metal drug [35].\u003c/p\u003e \u003cp\u003eIt is generally accepted that Cd\u003csup\u003e2+\u003c/sup\u003e ions, unlike other elements (Zn\u003csup\u003e2+\u003c/sup\u003e, Se\u003csup\u003e2-\u003c/sup\u003e and Mg\u003csup\u003e2+\u003c/sup\u003e), are not necessary for the human body and do not participate in known enzymatic processes. On the other hand, some authors have obtained evidence of cell apoptosis as a result of Cd\u003csup\u003e2+\u003c/sup\u003e intoxication; its ability to cause DNA fragmentation is also known [37\u0026ndash;39]. Cd\u003csup\u003e2+\u003c/sup\u003e ions are considered to be quite toxic, but it has been demonstrated that their toxicity depends on the compound used and therefore can be controlled by complexation [40]. In this context Cd(II)-based coordination compounds with N-containing ligands such as 1,10-phenanthroline may be useful for the development of new antimicrobial agents. The activity order is [Cu(bpy)(phen)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e]Cl\u003csub\u003e2\u003c/sub\u003e \u0026gt; [Co(bpy)(phen)\u003csub\u003e2\u003c/sub\u003e](NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e \u0026gt; [Zn(bpy)\u003csub\u003e2\u003c/sub\u003e(phen)]Cl\u003csub\u003e2\u003c/sub\u003e [41\u0026ndash;43].\u003c/p\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR spectra of 1,10-phenanthroline and coordinated 1,10-phenanthroline in diamagnetic d-element complexes have been studied in various publications, covering such aspects as the effect on the position and shape of the signals of the central ion of the complexing agent, as well as solvents. The indication of \u003csup\u003e1\u003c/sup\u003eH NMR spectra in such systems allows one to draw certain conclusions about the structure of compounds. The \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of [Pt(phen)Cl\u003csub\u003e2\u003c/sub\u003e] is discussed in [44]. In [45], six groups of signals were identified for 1,10-phenanthroline in CDCl\u003csub\u003e3\u003c/sub\u003e in \u003csup\u003e13\u003c/sup\u003eC NMR spectra. For the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of 1,10-phenanthroline in CDCl\u003csub\u003e3\u003c/sub\u003e (300 MHz), the following sets of signals are given (chemical shift values δ ppm, relative intensity is given in parentheses): 7.56 (231), 7.57 (237), 7.59 (254), 7.60 (257); 8.18 (263), 8.19 (267), 8.21 (258), 8.22 (1000); 9.17 ((258), 9.18 (259), 9.19 (250) [46]. In [47] the following assignments were made for the signals of 1,10-phenanthroline in \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra: δ\u003csub\u003eH\u003c/sub\u003e (300.1 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) 9.18 (dd, \u003cem\u003eJ\u003c/em\u003e 4.2,1.8, 2H, H2\u0026thinsp;+\u0026thinsp;H9), 8.23 (dd, \u003cem\u003eJ\u003c/em\u003e 8.1, 1.5, 2H, H4\u0026thinsp;+\u0026thinsp;H7), 7.77 (s, 2H, H5\u0026thinsp;+\u0026thinsp;H6), 7.62 (dd, \u003cem\u003eJ\u003c/em\u003e 7.8, 4.3, 2H, H3\u0026thinsp;+\u0026thinsp;H8). δ\u003csub\u003eC\u003c/sub\u003e (75 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e) 123.1 (C3\u0026thinsp;+\u0026thinsp;C8), 126.6 (C5\u0026thinsp;+\u0026thinsp;C6), 128.7 (C13\u0026thinsp;+\u0026thinsp;C14), 136.0 (C4\u0026thinsp;+\u0026thinsp;C7), 146.3 (C11\u0026thinsp;+\u0026thinsp;C12), 150.4 (C2\u0026thinsp;+\u0026thinsp;C9). Detailed analysis of \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra 1,10-phenanthroline was carried out in [48]. For 1,10-phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO and [Mg(phen)\u003csub\u003e3\u003c/sub\u003e](NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026bull;9H\u003csub\u003e2\u003c/sub\u003eO in DMSO-D\u003csub\u003e6\u003c/sub\u003e the following values of δ\u003csub\u003eH\u003c/sub\u003e (ppm): 2,9- 9.12 (d), 4,7- 8.52 (d), 5,6- 8.02 (s), 3,8- 7.80 (q); 2,9- 8.95, 4,7- 8.88, 5,6- 8.33 (s), 3,8\u0026ndash;8.00 (q) were found [49].\u003c/p\u003e \u003cp\u003eIn this work, the \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of mixed-ligand acetate complexes of Zn(II) and Cd(II) with 1,10-phenanthroline were systematically studied for the first time.\u003c/p\u003e "},{"header":"2 Experimental Part","content":"\u003cdiv id=\"Sec2\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials and Methods\u003c/h2\u003e \u003cdiv id=\"Sec3\" class=\"Section3\"\u003e \u003ch2\u003e2.1.1 Starting Materials\u003c/h2\u003e \u003cp\u003e1,10-Phenanthroline monohydrate phen\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO (clean for analysis, production in Germany) was purchased in LenReactiv (192240, St. Petersburg, Russia, 6th Preport passage, 8), zinc acetate dihydrate Zn(AcO)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO (chemically pure, production in Russia), cadmium acetate dihydrate Cd(AcO)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO (chemically pure, production in Russia) \u0026mdash; in NevaReactiv (195043, St. Petersburg, Russia, Kapsulnoe highway, 45).\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e mononuclear 1,10-phenanthroline acetate complexes\u003c/h2\u003e \u003cp\u003eThe synthesis of mononuclear 1,10-phenanthroline complexes of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e \u003cb\u003eM(phen)\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e(OAc)\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u0026bull;\u003cb\u003e2H\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1\u0026ndash;3) was carried out by complexation of M(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO acetates with 1,10-phenanthroline monohydrate in aqueous solutions at a temperature of 90\u0026ndash;95 \u0026deg; C (n\u0026thinsp;=\u0026thinsp;1), or in melts at a temperature of 110\u0026ndash;115 \u0026deg; C (n\u0026thinsp;=\u0026thinsp;2, 3), heating mixtures of starting substances for about 1 hour in stoichiometric ratios. According to the data of the elemental analysis, the composition of the compounds corresponds to the formulas given (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e, a \u003cb\u003eM\u0026thinsp;=\u0026thinsp;Zn\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e, \u003cb\u003eb M\u0026thinsp;=\u0026thinsp;Cd\u003c/b\u003e\u003csup\u003e\u003cb\u003e2+\u003c/b\u003e\u003c/sup\u003e). The IR spectra of substances (in tablets with KBr, 2000\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e-1\u003c/sup\u003e) indicate the coordination of 1,10-phenanthroline to Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, respectively. The compounds are highly soluble in water at room temperature. The resulting solutions are colorless.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of diacetato-mono(1,10-phenanthroline)zinc dihydrate Zn(phen)(OAc)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e\u0026bull; 2H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003c/p\u003e \u003cp\u003eA stoichiometric equimolar amount (1 mol: 1 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was gradually added to a concentrated aqueous solution of zinc acetate dihydrate Zn(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO at a temperature of 90\u0026ndash;95 \u003csup\u003eo\u003c/sup\u003eC and stirring. This forms a colorless solution. Then heating was continued for about 1 hour. With partial evaporation of water, the colorless complex Zn(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO crystallized. It was separated and dried at room temperature. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 44.7, H 4.4, N 7.2. For Zn(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e14\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn, calculated, %: C 44.92, H 4.81, N 7.49.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of diacetato-bis(1,10-phenanthroline)zinc dihydrate Zn(phen)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(OAc)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e\u0026bull;2H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003c/p\u003e \u003cp\u003eA mixture of solid zinc acetate dihydrate Zn(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO and a stoichiometric amount (1 mol: 2 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was thermostated at a temperature of 110\u0026ndash;115 \u003csup\u003eo\u003c/sup\u003eC for about 1 hour. A colorless glassy compound Zn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO is formed. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 44.7, H 4.4, N 7.2. For Zn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e26\u003c/sub\u003eH\u003csub\u003e26\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn, calculated, %: C 44.92, H 4.81, N 7.49.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of tris(1,10-phenanthroline)zinc(II) acetate dihydrate [Zn(phen)\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e](OAc)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e\u0026bull; 2H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003c/p\u003e \u003cp\u003eA mixture of solid zinc acetate dihydrate Zn(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO and a stoichiometric amount (1 mol: 3 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was thermostated at a temperature of 110\u0026ndash;115 \u003csup\u003eo\u003c/sup\u003eC for about 1 hour. A colorless glassy compound [Zn(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO is formed. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 62.0, H 4.4, N 11.2. For [Zn(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e38\u003c/sub\u003eH\u003csub\u003e34\u003c/sub\u003eN\u003csub\u003e6\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn, calculated, %: C 62.12, H 4.63, N 11.44.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of diacetato-mono(1,10-phenanthroline)cadmium dihydrate Cd(phen)(OAc)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e\u0026bull; 2H\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003c/p\u003e \u003cp\u003eA stoichiometric amount (1 mol: 1 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was gradually added to a concentrated aqueous solution of cadmium acetate dihydrate Cd(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO at a temperature of 90\u0026ndash;95 \u003csup\u003eo\u003c/sup\u003eC and stirring. This forms a colorless solution. Heating was then continued for about 1 hour. Upon partial evaporation of water, the colorless complex Cd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO crystallizes. It was separated and dried at room temperature. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 39.4, H 4.1, N 6.4. For Cd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e14\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCd, calculated, %: C 39.62, H 4.25, N 6.60.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of diacetato-bis(1,10-phenanthroline)cadmium dihydrate Cd(phen)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(OAc)\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e\u0026bull;2H\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003c/p\u003e \u003cp\u003eA mixture of solid cadmium acetate dihydrate Cd(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO and a stoichiometric amount (1 mol: 2 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was thermostated at a temperature of 110\u0026ndash;115 \u003csup\u003eo\u003c/sup\u003eC for about 1 hour. A colorless glassy compound Cd(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO is formed. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 51.4, H 4.3, N 9.2. For Cd(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e26\u003c/sub\u003eH\u003csub\u003e26\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCd, calculated, %: C 51.65, H 4.30, N 9.27.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of tris(1,10-phenanthroline)cadmium(II) acetate dihydrate [Cd(phen)\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e] (OAc)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e\u0026bull;2H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003c/p\u003e \u003cp\u003eA mixture of solid cadmium acetate dihydrate Cd(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO and a stoichiometric amount (1 mol: 3 mol) of 1,10-phenanthroline monohydrate phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO was thermostated at a temperature of 110\u0026ndash;115 \u003csup\u003eo\u003c/sup\u003eC for about 1 hour. A colorless glassy compound [Cd(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO is formed. The compound is highly soluble in water and soluble in DMSO.\u003c/p\u003e \u003cp\u003eElemental analysis\u0026ndash;found, %: С 62.0, H 4.4, N 11.2. For [Cd(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e38\u003c/sub\u003eH\u003csub\u003e34\u003c/sub\u003eN\u003csub\u003e6\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCd, calculated, %: C 62.12, H 4.63, N 11.44.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 NMR Measurements\u003c/h2\u003e \u003cp\u003eMeasurements of the NMR spectra of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e complexes were carried out on the NMR spectrometer Bruker 500 MHz Avance III at the Magnetic Resonance Methods of Investigation Resource Center (MRMI RC) of the St. Petersburg Science Park of St. Petersburg State University, and also at the Bioengineering Center of St. Petersburg State Technological Institute (Technical University) on the NMR spectrometer Bruker BioSpin AG, Avance III HD 400 MHz.\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and Discussion","content":"\u003cp\u003eThe production of glassy nanoscale polymorphic binuclear chromophore 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e with pharmacophore bridging ligands \u003cstrong\u003e(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eM(\u0026micro;-N-biphen)M(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e \u003cstrong\u003e(n\u0026thinsp;=\u0026thinsp;0\u0026ndash;2)\u003c/strong\u003e was carried out using the original methodology of metal-assisted non-dehydrogenative C(sp\u003csup\u003e2\u003c/sup\u003e)\u003cem\u003eH\u003c/em\u003e coupling coordinated 1,10-phenanthroline in acetate complexes of d-elements [7\u0026ndash;9]. The synthesis of binuclear chromophore 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e was carried out in melts at a temperature of 200\u0026ndash;205\u0026deg;C, heating the corresponding simple mononuclear 1,10-phenanthroline precursors for 25\u0026ndash;30 minutes. As a result of the C(sp\u003csup\u003e2\u003c/sup\u003e)\u003cem\u003eH\u003c/em\u003e coupling of coordinated 1,10-phenanthroline, after cooling the black-purple melts, the compounds were obtained in a glassy state. 1,10-Phenanthrocyanines (bi-1,10-phenanthrolylenes) are highly soluble in chloroform, DMF and DMSO at room temperature with the formation of intensely colored purple-violet solutions. IR spectra of substances (in tablets with KBr, 2000\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e-1\u003c/sup\u003e) confirm the coordination of 1,10-phenanthroline to Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, respectively. For example, Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e shows the structure of \u003cstrong\u003eM(\u0026micro;-N-biphen)M(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e, \u003cstrong\u003eM\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e2+\u003c/strong\u003e\u003c/sup\u003e = \u003cstrong\u003eZn\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e2+\u003c/strong\u003e\u003c/sup\u003e, \u003cstrong\u003eCd\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e2+\u003c/strong\u003e\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of glassy binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes or N-heterophenylenes) of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e show signal sets of a significantly more complex structure than mononuclear acetate 1,10-phenanthroline precursors corresponding to both 1,10-phenanthroline ligands and bridged 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes). The latter contain \u003cem\u003edihydro\u003c/em\u003e-bi-1,10-phenanthroline fragments, which appear in the \u003csup\u003e1\u003c/sup\u003eH NMR spectra in the range 5.0-7.5 ppm. The detection of signals belonging to the bridge chromophores of \u003cstrong\u003e\u0026micro;-biphen\u003c/strong\u003e was performed on the basis of NMR spectra of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e (Fig. 2) compounds that do not contain pure 1,10-phenanthroline ligands.\u003c/p\u003e\n\u003cp\u003eThe study of \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of glassy binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes or N-heterophenylenes) of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e in DMSO-D\u003csub\u003e6\u003c/sub\u003e solutions shows that, compared with their simple mononuclear precursors, binuclear chromophore complexes contain bridging ligands of a significantly more complex nature than 1,10-phenanthroline. These are \u003cem\u003eelectron-rich\u003c/em\u003e pharmacophore 1,10-phenanthrocyanine C\u0026ndash;C-dimers. These bridging ligands modify the biocidal action of mononuclear 1,10-phenanthroline precursors. The studied binuclear compounds can be used as modulators of microbial activity, in particular, as \u0026laquo;soft\u0026raquo; biostatic antifouling agents.\u003c/p\u003e\n\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\n \u003ch2\u003e3.1 Investigation of Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e mononuclear 1,10-phenanthroline acetate complexes by NMR Specrtoscopy\u003c/h2\u003e\n \u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of solutions in D\u003csub\u003e2\u003c/sub\u003eO and deuterated organic solvent DMSO-D\u003csub\u003e6\u003c/sub\u003e of mononuclear Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e 1,10-phenanthroline complexes: \u003cstrong\u003eM(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u0026bull;\u003cstrong\u003e2H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1\u0026ndash;3, \u003cstrong\u003e1\u0026ndash;3 a\u003c/strong\u003e, \u003cstrong\u003eb\u003c/strong\u003e) (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e) of binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) \u003cstrong\u003e(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eM(\u0026micro;-biphen)M(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e (n\u0026thinsp;=\u0026thinsp;0\u0026ndash;2) with pharmacophore bridging ligands were studied.\u003c/p\u003e\n \u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of simple mononuclear 1,10-phenanthroline acetates of Zn\u003csup\u003e2+\u003c/sup\u003e \u003cstrong\u003e1\u0026ndash;3\u003c/strong\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e \u003cstrong\u003e1a-3b\u003c/strong\u003e in D\u003csub\u003e2\u003c/sub\u003eO and DMSO-D\u003csub\u003e6\u003c/sub\u003e contain a set of signals characteristic of coordinated 1,10-phenanthroline. The coordination of 1,10-phenanthroline to Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions has almost no effect on the chemical shifts of the signals of hydrogen atoms in the heteroaromatic region. While the nature of the solvent significantly affects them. And during the transition from D\u003csub\u003e2\u003c/sub\u003eO to DMSO-D\u003csub\u003e6\u003c/sub\u003e, the proton signals of the heteroaromatic ring shift to a low field. The largest shifts in proton signals were detected for the binary solvent D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1).\u003c/p\u003e\n \u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of solutions in D\u003csub\u003e2\u003c/sub\u003eO and deuterated organic solvent DMSO-D\u003csub\u003e6\u003c/sub\u003e of mononuclear Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e 1,10-phenanthroline complexes: \u003cstrong\u003eM(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e \u003cstrong\u003e(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u0026bull;\u003cstrong\u003e2H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e2+\u003c/sup\u003e и Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1\u0026ndash;3, \u003cstrong\u003e1\u0026ndash;3 a\u003c/strong\u003e, \u003cstrong\u003eb\u003c/strong\u003e) (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e) of binuclear 1,10-phenanthrocyanines (bi-1,10-phenanthrolylenes) \u003cstrong\u003e(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eM(\u0026micro;-biphen)M(phen)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e(OAc)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e (n\u0026thinsp;=\u0026thinsp;0\u0026ndash;2) with pharmacophore bridging ligands were studied.\u003c/p\u003e\n \u003cp\u003eShift in the low field of heteroaromatic proton signals in 1.10-phenanthroline ring in \u003csup\u003e1\u003c/sup\u003eH NMR spectra of complexes in the sequence: 3,8- \u0026lt; 5,6- \u0026lt; 4,7- \u0026lt; 2,9 ( 4\u0026ndash;8, 10, 12, Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, Scheme 1) is consistent with an increase in the electron acceptor effect of N atoms in 1,10-phenanthroline ring, which it is implemented in the same sequence.\u003c/p\u003e\n \u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of simple mononuclear 1,10-phenanthroline acetates of Zn\u003csup\u003e2+\u003c/sup\u003e \u003cstrong\u003e1a\u003c/strong\u003e-\u003cstrong\u003e3a\u003c/strong\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e \u003cstrong\u003e1b\u003c/strong\u003e-\u003cstrong\u003e3b\u003c/strong\u003e in D\u003csub\u003e2\u003c/sub\u003eO and DMSO-D\u003csub\u003e6\u003c/sub\u003e contain a set of signals characteristic of coordinated 1,10-phenanthroline (Tables \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e). The coordination of 1,10-phenanthroline to Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions has almost no effect on the chemical shifts of the signals of hydrogen atoms in the heteroaromatic region. While the nature of the solvent significantly affects them. And during the transition from D\u003csub\u003e2\u003c/sub\u003eO to DMSO-D\u003csub\u003e6\u003c/sub\u003e for coordination-unsaturated complexes \u003cstrong\u003e1a\u003c/strong\u003e, \u003cstrong\u003e2a\u003c/strong\u003e, \u003cstrong\u003e1b\u003c/strong\u003e and \u003cstrong\u003e2b\u003c/strong\u003e the proton signals of the heteroaromatic ring shift to a low field. The largest shifts in proton signals were detected for the binary solvent D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1).\u003c/p\u003e\n \u003cp\u003eWhen analyzing the \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of compounds, attention should be paid to the fact that the NMR parameters of acetate groups (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e) are close for complexes and simple salts (Fig. \u003cspan class=\"InternalRef\"\u003e13\u003c/span\u003e, 14).\u003c/p\u003e\n \u003cp\u003eThis should indicate that the acetate groups in the solutions of the complexes are in all cases external. That is, dissociation and solvation reactions (S \u0026ndash; solvent, D\u003csub\u003e2\u003c/sub\u003eO or DMSO-D\u003csub\u003e6\u003c/sub\u003e) occur rapidly in solutions of complexes:\u003c/p\u003e\n \u003cp\u003eM(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e \u0026rarr; M(phen)\u003csub\u003en\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e + 2 OAc\u003csup\u003e\u0026minus;\u003c/sup\u003e (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e2+\u003c/sup\u003e, Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1, 2)\u003c/p\u003e\n \u003cp\u003eM(phen)\u003csup\u003e2+\u003c/sup\u003e + 4 S\u0026rarr; [M(phen)S\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003eM(phen)\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e + 2 S\u0026rarr; [M(phen)\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003e[M(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e \u0026rarr; [M(phen)\u003csub\u003e3\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e + 2 OAc\u003csup\u003e\u0026minus;\u003c/sup\u003e (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e2+\u003c/sup\u003e, Cd\u003csup\u003e2+\u003c/sup\u003e)\u003c/p\u003e\n \u003cp\u003eThe coordination of DMSO-D\u003csub\u003e6\u003c/sub\u003e to Zn\u003csup\u003e+\u0026thinsp;2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, as soft Lewis acids, should be carried out through its soft donor atom S in accordance with the principle of hard and soft acids and bases (HSAB) [32]\u003c/p\u003e\n \u003cp\u003eUnexpected was the fact that in the case of the M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO complexes (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e+\u0026thinsp;2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1,2), the effect on the chemical shifts of the \u0026delta;\u003csub\u003eH\u003c/sub\u003e protons in the heteroaromatic region of the \u003csup\u003e1\u003c/sup\u003eH NMR spectra for the DMSO-D\u003csub\u003e6\u003c/sub\u003e\u0026ndash;D\u003csub\u003e2\u003c/sub\u003eO (1:1) mixture was maximal, which is unprecedented. For D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e mixture, there is a strong shift of \u0026delta;\u003csub\u003eH\u003c/sub\u003e values to a low field (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). This is most likely due to the formation of solvates in solutions containing both D\u003csub\u003e2\u003c/sub\u003eO (S1) and DMSO-D\u003csub\u003e6\u003c/sub\u003e (S2):\u003c/p\u003e\n \u003cp\u003eM(phen)\u003csup\u003e2+\u003c/sup\u003e + 2 S1\u0026thinsp;+\u0026thinsp;2 S2 \u0026rarr; [M(phen)S1\u003csub\u003e2\u003c/sub\u003eS2\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003eM(phen)\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e + S1\u0026thinsp;+\u0026thinsp;S2\u0026rarr; [M(phen)\u003csub\u003e2\u003c/sub\u003eS1S2]\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e\n \u003cp\u003eFor \u003csup\u003e13\u003c/sup\u003eC signals such an offset in D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e mixture is not observed (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e\n\u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eIt was found that the chemical shifts of the δ\u003csub\u003eH\u003c/sub\u003e protons of the heteroaromatic rings of 1,10-phenanthroline are sensitive to coordination with Zn\u003csup\u003e+\u0026thinsp;2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, but the type of solvent has the greatest effect on δ\u003csub\u003eH\u003c/sub\u003e. For M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO (М = Zn\u003csup\u003e+\u0026thinsp;2\u003c/sup\u003e and Cd\u003csup\u003e2\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1, 2) complexes, the maximum shift to a weak field of δ\u003csub\u003eH\u003c/sub\u003e values occurs for the mixed solvent D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e. For complexes [M(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO in the solvent D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e, on the contrary, there is a very weak shift of the values of δ\u003csub\u003eH\u003c/sub\u003e in a strong field compared with the values for DMSO-D\u003csub\u003e6\u003c/sub\u003e and in a weak field compared with the values in D\u003csub\u003e2\u003c/sub\u003eO. The difference in the \u003csup\u003e1\u003c/sup\u003eH NMR spectral pattern for compounds M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO (n\u0026thinsp;=\u0026thinsp;1,2) and [M(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO should be associated with the coordination saturation of the latter, for which the insertion of a solvent \u0026ndash; D\u003csub\u003e2\u003c/sub\u003eO or DMSO-D\u003csub\u003e6\u003c/sub\u003e into the internal coordination sphere is practically impossible While the complexes M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO (n\u0026thinsp;=\u0026thinsp;1, 2) are coordination-unsaturated structures and allow solvent molecules to penetrate into their internal coordination sphere by substitution of acetate groups\u003csup\u003e\u0026minus;\u003c/sup\u003eOAc.\u003c/p\u003e \u003cp\u003eIt is unexpected that in the case of M(phen)n(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO complexes (M\u0026thinsp;=\u0026thinsp;Zn\u003csup\u003e+\u0026thinsp;2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e, n\u0026thinsp;=\u0026thinsp;1, 2), the effect on the chemical shifts of δ\u003csub\u003eH\u003c/sub\u003e protons in the heteroaromatic region of the \u003csup\u003e1\u003c/sup\u003eH NMR spectra for D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1 : 1) mixture is maximal, which is unprecedented.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e VND wrote a manuscript, synthesized compounds, participated in the formulation of the concept (while performing the main role), AGI participated in the formulation of the concept, INT, VIV, YAK, IBG, TBP participated in the synthesis of compounds, their characterization and depicted structural formulas. All authors have reviewed the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u0026nbsp;\u003c/strong\u003eThe work was carried out at I.V. Grebenschikov Institute of Silicate Chemistry of the Russian Academy of Sciences within the framework of the theme of the state budget: \u0026ldquo;Physical-chemical bases of inorganic synthesis of micro- and nanostructured non-organic, organo-non-organic and ceramic materials and coatings for bio-, energy- and resource-saving technologies.\u0026rdquo; (1023033000122-7-1.4.3).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of Data and Materials\u003c/strong\u003e The materials are available in the databases of I.V. Grebenschikov Institute of the Silicate Chemistry of the Russian Academy of Sciences and the Resource Center \u0026ldquo;Magnetic Resonance Research Methods\u0026rdquo; of St. Petersburg State University, and also at the Bioengineering Center of St. Petersburg State Technological Institute (Technical University).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConfict of interest\u003c/strong\u003e The authors declare that they have no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical approval\u003c/strong\u003e Not applicable.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eV.N. Demidov, V.G. Puzenko, A.I. Savinova, N.S. Panina, T.B. Pakhomova, L.N. Vedeneeva, S.A. Simanova, Electron-rich metal phenanthrocyanine - new class of tetraazachromophore complexes of d-elements. News MIFCT, Fine Chem. Technol. \u003cstrong\u003e2\u003c/strong\u003e (3), 36-43 (2007). 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Chem. \u003cstrong\u003e629\u003c/strong\u003e (1), 12-14 (2003). https://doi.org/10.1002/zaac.200390005\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003e\u003cstrong\u003eTable 1 \u0026nbsp;\u0026nbsp;\u003c/strong\u003e1,10-phenanthroline ring parameters of \u003csup\u003e1\u003c/sup\u003eH NMR spectra of Zn(II) and Cd(II) complexes with 1,10-phenanthroline\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"680\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"8.370044052863436%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eNo.\u003c/p\u003e\n \u003cp\u003eof comp.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.431718061674008%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCompound\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.80323054331865%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"51.395007342143906%\" colspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003eThe chemical shifts of H atoms in 1,10-phenanthroline ring, \u0026delta;\u003csub\u003eH\u003c/sub\u003e (ppm)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"100%\" colspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003eThe position of the H atoms in the cycle of 1,10-phenanthroline (Scheme 1)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.355300859598852%\" valign=\"top\"\u003e\n \u003cp\u003e3,8-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"24.355300859598852%\" valign=\"top\"\u003e\n \u003cp\u003e5,6-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.93409742120344%\" valign=\"top\"\u003e\n \u003cp\u003e4,7-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"24.355300859598852%\" valign=\"top\"\u003e\n \u003cp\u003e2,9-\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"8.382352941176471%\" valign=\"top\"\u003e\n \u003cp\u003e1a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e2a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e3b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.470588235294116%\" valign=\"top\"\u003e\n \u003cp\u003eZn(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eZn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e[Cd(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1,10-phen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.823529411764707%\" valign=\"top\"\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"12.5%\" valign=\"top\"\u003e\n \u003cp\u003e7.36\u003c/p\u003e\n \u003cp\u003e8.07\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.94\u003c/p\u003e\n \u003cp\u003e9.97\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.21\u003c/p\u003e\n \u003cp\u003e7.99\u003c/p\u003e\n \u003cp\u003e10.07\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.46\u003c/p\u003e\n \u003cp\u003e7.86, 7.87\u003c/p\u003e\n \u003cp\u003e7.75\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.72\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"12.5%\" valign=\"top\"\u003e\n \u003cp\u003e7.63, 7.88\u003c/p\u003e\n \u003cp\u003e8.21\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.12\u003c/p\u003e\n \u003cp\u003e10.09\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.54\u003c/p\u003e\n \u003cp\u003e8.16\u003c/p\u003e\n \u003cp\u003e10.18\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.52, 7.54\u003c/p\u003e\n \u003cp\u003e8.05\u003c/p\u003e\n \u003cp\u003e7.88\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.823529411764707%\" valign=\"top\"\u003e\n \u003cp\u003e8.13, 8.34\u003c/p\u003e\n \u003cp\u003e8.85\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.72\u003c/p\u003e\n \u003cp\u003e10.29\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e7.99\u003c/p\u003e\n \u003cp\u003e8.74, 8.76\u003c/p\u003e\n \u003cp\u003e10.78\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.17, 8.19\u003c/p\u003e\n \u003cp\u003e8.54, 8.61\u003c/p\u003e\n \u003cp\u003e8.50, 8.52\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.44\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"12.5%\" valign=\"top\"\u003e\n \u003cp\u003e8.47, 8.74\u003c/p\u003e\n \u003cp\u003e9.06\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e9.03\u003c/p\u003e\n \u003cp\u003e10.90\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.60\u003c/p\u003e\n \u003cp\u003e9.06\u003c/p\u003e\n \u003cp\u003e11.08\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e8.39\u003c/p\u003e\n \u003cp\u003e8.91\u003c/p\u003e\n \u003cp\u003e8.65\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e9.09\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e*) in mixture D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1)\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 2 \u0026nbsp;\u0026nbsp;\u003c/strong\u003e1,10-phenanthroline ring parameters of \u003csup\u003e13\u003c/sup\u003eC NMR spectra of Zn(II) and Cd(II) complexes with 1,10-phenanthroline and 1,10-phenanthroline monohydrate\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"5.561277033985582%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003eNo. of comp.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.4346035015448%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCompound\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.122554067971164%\" rowspan=\"3\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"64.88156539649846%\" colspan=\"6\" valign=\"top\"\u003e\n \u003cp\u003eThe chemical shifts of C atom in 1,10-phenanthroline ring, \u0026delta;\u003csub\u003eC\u003c/sub\u003e (ppm)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"100%\" colspan=\"6\" valign=\"top\"\u003e\n \u003cp\u003eThe position of the C atoms in the cycle of 1,10-phenanthroline (Scheme 1)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"17.11568938193344%\" valign=\"top\"\u003e\n \u003cp\u003e3,8-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.11568938193344%\" valign=\"top\"\u003e\n \u003cp\u003e5,6-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.11568938193344%\" valign=\"top\"\u003e\n \u003cp\u003e13,14-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.700475435816166%\" valign=\"top\"\u003e\n \u003cp\u003e4,7-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"14.896988906497622%\" valign=\"top\"\u003e\n \u003cp\u003e11,12-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"15.055467511885896%\" valign=\"top\"\u003e\n \u003cp\u003e2,9-\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"5.555555555555555%\" valign=\"top\"\u003e\n \u003cp\u003e1a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e2a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e3b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.415637860082306%\" valign=\"top\"\u003e\n \u003cp\u003eZn(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eZn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e[Cd(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003ephen\u0026bull;H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.11111111111111%\" valign=\"top\"\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-d\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.11111111111111%\" valign=\"top\"\u003e\n \u003cp\u003e125.16\u003c/p\u003e\n \u003cp\u003e126.09\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e125.23\u003c/p\u003e\n \u003cp\u003e128.07\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e124.84\u003c/p\u003e\n \u003cp\u003e125.38\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e124.97\u003c/p\u003e\n \u003cp\u003e125.66\u003c/p\u003e\n \u003cp\u003e125.55\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e123.68\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.11111111111111%\" valign=\"top\"\u003e\n \u003cp\u003e126.32\u003c/p\u003e\n \u003cp\u003e127.43\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e127.34\u003c/p\u003e\n \u003cp\u003e129.56\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e126.43\u003c/p\u003e\n \u003cp\u003e127.41\u003c/p\u003e\n \u003cp\u003e129.59\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e127.06\u003c/p\u003e\n \u003cp\u003e126.91\u003c/p\u003e\n \u003cp\u003e127.58\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e127.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.11111111111111%\" valign=\"top\"\u003e\n \u003cp\u003e128.25\u003c/p\u003e\n \u003cp\u003e128.87\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e128.88\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e128.49\u003c/p\u003e\n \u003cp\u003e128.87\u003c/p\u003e\n \u003cp\u003e131.31\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e129.33\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e129.56\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e128.89\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"12.139917695473251%\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e140.18\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e138.67\u003c/p\u003e\n \u003cp\u003e142.65\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e139.39\u003c/p\u003e\n \u003cp\u003e139.11\u003c/p\u003e\n \u003cp\u003e141.97\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e139.97\u003c/p\u003e\n \u003cp\u003e139.79\u003c/p\u003e\n \u003cp\u003e140.19\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e136.55\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"9.670781893004115%\" valign=\"top\"\u003e\n \u003cp\u003e139.79\u003c/p\u003e\n \u003cp\u003e140.64\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e142.62\u003c/p\u003e\n \u003cp\u003e150.83\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e149.35\u003c/p\u003e\n \u003cp\u003e141.07\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e140.45\u003c/p\u003e\n \u003cp\u003e139.79\u003c/p\u003e\n \u003cp\u003e140.86\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e145.89\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"9.77366255144033%\" valign=\"top\"\u003e\n \u003cp\u003e148.48\u003c/p\u003e\n \u003cp\u003e150.09\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e150.04\u003c/p\u003e\n \u003cp\u003e150.83\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e149.35\u003c/p\u003e\n \u003cp\u003e150.49\u003c/p\u003e\n \u003cp\u003e152.23\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e149.39\u003c/p\u003e\n \u003cp\u003e149.12\u003c/p\u003e\n \u003cp\u003e149.99\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e150.39\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e*) in mixture D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1)\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 3 \u0026nbsp;\u0026nbsp;\u003c/strong\u003eAcetate groups parameters of \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra of Zn(II) and Cd(II) acetate complexes with 1,10-phenanthroline and Cd(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"8.463949843260188%\" valign=\"top\"\u003e\n \u003cp\u003eNo.\u003c/p\u003e\n \u003cp\u003eof comp.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.0564263322884%\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCompound\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.24137931034483%\" valign=\"top\"\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.905956112852664%\" valign=\"top\"\u003e\n \u003cp\u003eThe chemical shifts of H atoms in CH\u003csub\u003e3\u003c/sub\u003e\u0026ndash;groups of CH\u003csub\u003e3\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026ndash;\u003c/sup\u003e anions, \u0026delta;\u003csub\u003eH\u003c/sub\u003e (ppm)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.322884012539184%\" valign=\"top\"\u003e\n \u003cp\u003eThe chemical shifts of C atoms in CH\u003csub\u003e3\u003c/sub\u003e\u0026ndash;groups of CH\u003csub\u003e3\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026ndash;\u003c/sup\u003e anions, \u0026delta;\u003csub\u003eC\u003c/sub\u003e (ppm)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.009404388714733%\" valign=\"top\"\u003e\n \u003cp\u003eThe chemical shifts of C atoms in CO\u003csub\u003e2\u003c/sub\u003e\u0026ndash;groups of CH\u003csub\u003e3\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026ndash;\u003c/sup\u003e anions, \u0026delta;\u003csub\u003eC\u003c/sub\u003e (ppm)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"8.463949843260188%\" valign=\"top\"\u003e\n \u003cp\u003e1a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e2a\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e3b\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"28.0564263322884%\" valign=\"top\"\u003e\n \u003cp\u003eZn(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eZn(phen)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCd(phen)(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e[Cd(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eCd(OAc)\u003csub\u003e2\u003c/sub\u003e\u0026bull;2H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.24137931034483%\" valign=\"top\"\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eD\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;\u003c/p\u003e\n \u003cp\u003eDMSO-D\u003csub\u003e6\u003c/sub\u003e*\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"19.905956112852664%\" valign=\"top\"\u003e\n \u003cp\u003e1.76 (1.59, 1.92)\u003c/p\u003e\n \u003cp\u003e1.79 (1.63, 1.94)\u003c/p\u003e\n \u003cp\u003e3.44\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1.76 (1.61, 1.92)\u003c/p\u003e\n \u003cp\u003e2.50\u003c/p\u003e\n \u003cp\u003e4.72, 3.91\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1.81\u003c/p\u003e\n \u003cp\u003e1.77 (1.61, 1.92)\u003c/p\u003e\n \u003cp\u003e2.50 (2.32, 2.68)\u003c/p\u003e\n \u003cp\u003e4.01 (3.85, 4.17)\u003c/p\u003e\n \u003cp\u003e4.72\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1.71\u003c/p\u003e\n \u003cp\u003e1.77 (1.59, 1.92)\u003c/p\u003e\n \u003cp\u003e1.74\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e1.79 (1.63, 1.94)\u003c/p\u003e\n \u003cp\u003e4.76\u003c/p\u003e\n \u003cp\u003e4.05 (4.02, 4.16)\u003c/p\u003e\n \u003cp\u003e4.72\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.322884012539184%\" valign=\"top\"\u003e\n \u003cp\u003e22.62\u003c/p\u003e\n \u003cp\u003e23.08\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e23.32\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e25.87\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e22.05\u003c/p\u003e\n \u003cp\u003e22.85\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e24.83\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e23.06\u003c/p\u003e\n \u003cp\u003e23.13\u003c/p\u003e\n \u003cp\u003e23.09\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e21.82\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e24.36\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.009404388714733%\" valign=\"top\"\u003e\n \u003cp\u003e181.58\u003c/p\u003e\n \u003cp\u003e177.89\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e177.69\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e181.80\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e181.36\u003c/p\u003e\n \u003cp\u003e176.81\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e181.57\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e181.14\u003c/p\u003e\n \u003cp\u003e179.84\u003c/p\u003e\n \u003cp\u003e178.34\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e181.62\u003c/p\u003e\n \u003cp\u003e\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e185.54\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e*) in mixture D\u003csub\u003e2\u003c/sub\u003eO\u0026ndash;DMSO-D\u003csub\u003e6\u003c/sub\u003e (1:1)\u003c/p\u003e"},{"header":"Schemes","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4553203/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4553203/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe NMR \u003csup\u003e1\u003c/sup\u003eН and \u003csup\u003e13\u003c/sup\u003eС spectra of Zn\u003csup\u003e+ 2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e acetate mononuclear complexes with 1,10-phenanthroline M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO (M = Zn\u003csup\u003e2+\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e, n = 1–3) for their solutions in DMSO-d\u003csub\u003e6\u003c/sub\u003e, D\u003csub\u003e2\u003c/sub\u003eO and mixture DMSO-D\u003csub\u003e6\u003c/sub\u003e–D\u003csub\u003e2\u003c/sub\u003eO were studied. The effect of the coordination centers and the solvents on the parameters of the \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra is considered. It is noted that the chemical shifts of the δ\u003csub\u003eH\u003c/sub\u003e protons of the heteroaromatic rings of 1,10-phenanthroline are sensitive to coordination with Zn\u003csup\u003e+ 2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e ions, but the type of solvent has the greatest effect on the δ\u003csub\u003eН\u003c/sub\u003e. For M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO (n = 1,2) complexes, the maximum shift to a weak field of δ\u003csub\u003eH\u003c/sub\u003e values occurs for the mixed solvent DMSO-D\u003csub\u003e6\u003c/sub\u003e–D\u003csub\u003e2\u003c/sub\u003eO. For complexes [M(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO in the mixed solvent DMSO-D\u003csub\u003e6\u003c/sub\u003e–D\u003csub\u003e2\u003c/sub\u003eO, on the contrary, there is a very weak shift of the values of δ\u003csub\u003eH\u003c/sub\u003e in a strong field compared with the values for DMSO-D\u003csub\u003e6\u003c/sub\u003e and in a weak field compared with the values in D\u003csub\u003e2\u003c/sub\u003eO. The difference in the \u003csup\u003e1\u003c/sup\u003eH NMR spectral pattern for compounds M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO (n = 1,2) and [M(phen)\u003csub\u003e3\u003c/sub\u003e](OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO should be associated with the coordination saturation of the latter, for which the insertion of a solvent – D\u003csub\u003e2\u003c/sub\u003eO or DMSO-D\u003csub\u003e6\u003c/sub\u003e into the internal coordination sphere is practically impossible While the complexes M(phen)\u003csub\u003en\u003c/sub\u003e(OAc)\u003csub\u003e2\u003c/sub\u003e•2H\u003csub\u003e2\u003c/sub\u003eO (n = 1,2) are coordination-unsaturated structures and allow solvent molecules to penetrate into their internal coordination sphere. Complexes of Zn\u003csup\u003e+ 2\u003c/sup\u003e and Cd\u003csup\u003e2+\u003c/sup\u003e with 1,10-phenanthroline were synthesized by complexation reactions.\u003c/p\u003e","manuscriptTitle":"Effect of the coordination centers and the solvents on the parameters of the 1H and 13C NMR spectra of biology active Zn+2 and Cd2+ acetate mononuclear complexes with chelating 1,10- phenanthroline","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-06-28 10:19:39","doi":"10.21203/rs.3.rs-4553203/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e6f43ca0-a430-42cc-bdf6-df34d9f57aad","owner":[],"postedDate":"June 28th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-06-28T10:19:39+00:00","versionOfRecord":[],"versionCreatedAt":"2024-06-28 10:19:39","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4553203","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4553203","identity":"rs-4553203","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}