Design and catalytic performance of a novel 2D copper MOF for green synthesis of tetrahydrobenzo[b]pyrans

Design and catalytic performance of a novel 2D copper MOF for green synthesis of tetrahydrobenzo[b]pyrans | 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 Article Design and catalytic performance of a novel 2D copper MOF for green synthesis of tetrahydrobenzo[b]pyrans Ehsan Joukar Bahaderani, Khosro Mohammadi, Payam Hayati, Jan Janczak This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6330783/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 03 Oct, 2025 Read the published version in Scientific Reports → Version 1 posted 13 You are reading this latest preprint version Abstract This study explores the development and use of a novel 2D MOF as a heterogeneous catalyst in organic synthesis. The phosphonocarboxylic acid m -PO 3 CH 2 C 6 H 4 CO 2 H ( L ) has been employed in the synthesis of a metal carboxyarylphosphonate. The 2D MOF [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n ( 1 ) was synthesized in both crystal ( 1 ) and nanostructure ( 1′ ) forms, characterized by X-ray single crystallography, SEM, TGA, FT-IR, PXRD, EDX, Mapping, and nitrogen adsorption–desorption, and employed for the efficient green synthesis of tetrahydrobenzo[b]pyrans (THBPs). The crystal structure features alternating inorganic and organic layers. The organic layers have supramolecular dimers of carboxylic acid groups, two molecules bonded to two inorganic layers. THBP yield optimization conditions were determined with water/ethanol as solvents, using a catalyst loading of 0.06 g for 95% yields. The synthesized catalyst demonstrated high catalytic activity, broad applicability to various aldehyde substrates, and notable reusability, maintaining high yields for up to seven cycles after the reaction. Compared with previous catalytic systems, compound ( 1′ ) exhibited superior efficiency and recyclability. These findings highlight the potential of this novel 2D MOF for facilitating environmentally friendly and efficient organic syntheses. Physical sciences/Chemistry Physical sciences/Nanoscience and technology Metal-organic framework Copper Phosphonocarboxylic acid Nanocatalyst Tetrahydrobenzo[b]pyran Multicomponent reaction Ultrasonic Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Introduction The growing demand for efficient and environmentally benign catalytic systems for organic synthesis has attracted significant research interest in metal-organic frameworks (MOFs) as catalysts [ 1 – 3 ]. These materials, characterized by metal ions coordinated to organic ligands, offer unique structural properties, such as tunable porosity, high surface area, and the ability to incorporate various functionalities into their frameworks [ 4 – 7 ]. MOFs have demonstrated considerable potential as heterogeneous catalysts, effectively facilitating a range of chemical transformations owing to their intrinsic properties, including the diffusion of reactants and stabilization of transition states [ 8 – 11 ]. Two-dimensional (2D) MOFs offer significant advantages over traditional three-dimensional (3D) MOFs by providing an increased surface area and enhanced reactant accessibility [ 12 – 15 ]. 2D MOFs are also better suited for film formation, making them useful for applications such as electrochemical energy storage, electrocatalysis, and photocatalysis [ 16 – 18 ]. 2D MOFs exhibit chemical and thermal stabilities comparable to or surpassing those of their three-dimensional counterparts [ 19 ]. These 2D structures have gained attention as potential replacements for costly noble metals, and are being explored for applications such as electrocatalysts and photocatalytic semiconductors [ 20 , 21 ]. The advantages of zeolites were first demonstrated, paving the way for their development in heterogeneous catalysis [ 22 ]. The distinctive characteristics of 2D MOFs, including their high surface area, accessibility, facile separation, and environmental recoverability, make them appealing candidates for catalytic applications. Some reports on this matter include (NH 4 ) 3 [In 3 Cl 2 (BPDC) 5 ] [ 23 ] and [Cd(PBA)(DMF)].DMF [ 24 ], Au-1@Ni-NMOF [ 25 ], Pd/NUS-SO 3 H [ 26 ], MF-Cu-BDC-8 [ 27 ], Ni-BDC MOF [ 28 ], and Cu(II)–5N 3 IP [ 29 ]. Ultrasonic waves in chemical synthesis improve reaction kinetics and product selectivity by causing cavitation, generating high temperatures and pressures, and promoting faster and more uniform reactant mixing [ 30 – 33 ]. Among the various classes of organic compounds, tetrahydrobenzo[b]pyrans (THBPs) are particularly noteworthy because of their prevalence in pharmaceuticals, agrochemicals, and natural products [ 34 ]. They exhibit diverse biological activities, including antibacterial, anticancer, and anti-inflammatory properties, making their synthesis an area of interest in medicinal chemistry [ 35 – 37 ]. Traditional synthetic routes for THBPs often involve multiple steps and the use of harsh reagents, leading to low yields and the generation of hazardous waste [ 38 , 39 ]. In chemistry, a significant technique known as the multicomponent reaction (MCR) involves the use of three or more starting materials to create valuable organic compounds [ 40 – 43 ]. THBPs have been synthesized using various catalytic systems; however, most of them have unfavorable characteristics, such as excessive catalyst loading, the use of hazardous organic solvents, high reaction temperatures, and catalyst non-recoverability [ 44 ]. As a result, one of the biggest challenges in this field is creating a novel and powerful catalytic mechanism to get over the aforementioned restrictions. By contributing to the understanding of catalytic pathways and the design of multifunctional materials, this study aims to support the development of greener methodologies in organic chemistry and expand the scope of MOFs for heterogeneous catalysis. This study reports the ultrasonic synthesis of a novel 2D MOF designed specifically as a heterogeneous catalyst for the efficient THBP synthesis. Experimental section Materials and methods All the chemicals and solvents were purchased from Sigma-Aldrich and Merck and used without further purification. The spectroscopic characterization of the synthesized compounds is achieved by recording Fourier transform infrared (FT-IR) spectra using a JASCO FT/IR-4600 spectrometer. Powder X-ray diffraction (PXRD) was perform applying an X’pert diffractometer created by Philips with monochromatized Cu K α radiation and scanning electron microscope (SEM) was performed using a VEGA3 microscope. Sonochemical experiments were performed using an US–Scientz-750F generator. Melting points were determined using a Krüss KSB1N-apparatus in open capillary tubes. Energy-dispersive X-ray spectroscopy (EDX) was performed using an EDAX-EDS Tescan-Vega2 instrument. Thermal gravimetric analysis (TGA) was carried out using a Perkin Elmer STA6000 apparatus. Brunauer-Emmett-Teller (BET) analysis was performed via Micromeritics Asap2020 apparatus. The SIGMA 2-16p centrifuge was effectively utilized in the process of separating catalysts from the mixtures. The intensity of single-crystal X-ray data for [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n (1) was measured using a Xcalibur four-circle κ geometry diffractometer with an Atlas two-dimensional area CCD detector at room temperature. The measurements were performed using graphite monochromatic Mo Kα radiation. Data collections, cell refinements, integration, correction for Lorenz and polarisation effects and absorption corrections were performed using the CrysAlisPro 1.171.42.93a program system [ 45 ]. Using Olex2 [ 46 ], the structure was solved by the direct methods using SHELXT [ 47 ] and refined with the SHELXL-2018/3 program [ 48 ]. The hydrogen atoms joined to aromatic carbon atoms were introduced in their geometrical positions and treated as rigid with U iso =1.2U eq (C). The positions of the hydrogen atoms linked to oxygen atoms were refined with U iso =1.5U eq (O). The final difference Fourier maps showed no peaks of chemical significance. Details of the data collection parameters, crystallographic data and final agreement parameters are collected in Table S1 . Diamond 3.0 program [ 49 ] was used for visualization of the structure. Synthesis of the single crystal ( 1 ) and nanoparticles ( 1′ ) Synthesis of [Cu(H 2 O)(m-PO 3 CH 2 C 6 H 4 CO 2 H)] n as MOF single crystals ( 1 ) To synthesize crystalline [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n , CuSO 4 .5H 2 O (0.1 mmol, 0.0249 g) and m -(phosphonomethyl)benzoic acid (MPMB) (0.1 mmol, 0.0216 g) were mixed in 10 mL of methanol and 1 mL deionized water and stirred at ambient temperature for 30 min. A Parr Teflon container was used to hold the reaction mixture, which was subsequently placed inside a stainless-steel tank. Following that, the tank was sealed in autoclave and heated to 110°C for a whole day. The reaction mixture was slowly cooled to room temperature, and blue-green crystals of [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n appeared and were identified using X-ray analysis. Sonochemical synthesis of [Cu(H 2 O)(m-PO 3 CH 2 C 6 H 4 CO 2 H)] n as MOF nanostructure ( 1′ ) Compound ( 1′ ) in powder form, [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n , was synthesized by combining CuSO 4 .5H 2 O (1 mmol, 0.249 g) with MPMB (1 mmol, 0.216 g) in a solution of 20 mL methanol and 2 mL deionized water. At room temperature, the mixture was stirred for half an hour. Specifically, the mixture was placed in a beaker and exposed to an ultrasonic frequency of 60 Hz for 30 min. The bath temperature was maintained at 50°C during the entire irradiation period. Following sonication, a light blue-green powder precipitate was observed, indicating the formation of the desired product. The solid was isolated via filtration and subsequently purified by washing with methanol, followed by copious amounts of deionized water. The resulting light-blue-green powder was characterized using appropriate analytical techniques to confirm its identity. Synthesis of THBPs using nanocatalyst ( 1′ ) This was accomplished by mixing nanocatalyst ( 1′ ) (0.06 g) with distilled water and ethanol in a 1:1 ratio (5 mL/5 mL), along with benzaldehyde (1 mmol), malononitrile (1.2 mmol), and dimedone (1 mmol). The resulting solution was then agitated vigorously at 35°C. The reaction’s development was tracked using thin-layer chromatography (TLC). After completing the reaction, catalyst ( 1′ ) was removed by centrifugation, and then hot ethanol was added. The final solution was placed in an ice bath to facilitate the crystallization or precipitation of the desired pure products. Results and discussion Synthetic perspective MPMB and copper(II) sulfate pentahydrate were combined in a methanol/water solvent combination to create the two-dimensional coordination complex [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n . The solvothermal technique was employed to grow single crystals of the new MOF, which were suitable for X-ray crystallographic analysis. Meanwhile, compound ( 1ʹ ) was obtained by reacting MPMB and copper(II) sulfate pentahydrate in a 1:1 stoichiometric ratio in methanol/water, with ultrasonic assistance, as illustrated in Fig. 1 . X-ray single crystal structure Crystal structure description The monoclinic centrosymmetric space group P2 1 /n was the crystallization structure for, as shown in Table S1 . The ORTEP view of ( 1 ) is depicted in Fig. 2 . Compound ( 1 ) exhibited a unit cell volume of 943.099 Å 3 . Examination of the inorganic layer revealed that Cu 2+ ions establish connections with the oxygen atoms of the phosphonate groups (Fig. 2 ). Water molecules were added to complete the coordination polyhedron surrounding the copper atoms, resulting in an octahedral arrangement of the oxygen atoms. The octahedron exhibited an irregular shape, with five of its bonds measuring between 1.938(4) Å and 2.231(4) Å, whereas one bond was significantly elongated at 2.581(4) Å. The tetrahedral structure surrounding each phosphorus atom consists of three oxygen atoms and one carbon atom. Each octahedron is connected at its corners to four adjacent octahedra, forming a structure resembling a perovskite layer. In the structure, the PO 3 C tetrahedra are connected to the CuO 6 octahedra by sharing one edge, forming the CuPO 7 C groups. These groups bear resemblance to the VPO 8 units found in Li 2 VO 2 PO 4 frameworks [ 50 ] and layered M(II)(RPO 3 ).H 2 O [ 51 ]. Furthermore, the PO 3 C tetrahedra shared a single corner with an additional octahedron. The perovskite layer undergoes significant deformation owing to this bonding, causing the octahedra to tilt dramatically in relation to the plane containing Cu 2+ ions. Compound ( 1 ) showcases a sturdy molecular framework. The structure is composed of alternating layers of inorganic and organic materials arranged in a systematic pattern (Fig. 3 ). The copper ion and ligand units of molecules covalently attached to others in a 2D structure (Fig. 3 a). Also, Hydrogen bonding interactions are notable within the 3D structure. The organic section exhibited supramolecular dimeric entities characterized by pairs of carboxylic acid groups (Fig. 3 b). The O1‧‧‧O2 interaction has a distance of 2.614(8) Å, whereas the O2–H21‧‧‧ O1 i bond forms an angle of 161°. Beyond the aforementioned supramolecular interactions, Table 1 details the hydrogen bonding involving water molecules coordinated to the copper atom. Table 1 Hydrogen-bond data (Å, º) in ( 1 ). D —H··· A D —H H··· A D ··· A D —H··· A O2—H21···O1 i 0.82 1.82 2.614 (8) 161 O6—H61···O3 ii 0.90 2.11 2.901 (6) 146 O6—H61···O5 0.90 2.31 2.908 (6) 124 O6—H62···O4 iii 0.90 2.20 3.068 (6) 161 O6—H62···O5 iv 0.90 2.36 2.905 (6) 119 Symmetry codes: ( i ) − x + 1, − y , − z + 1; ( ii ) x , y − 1, z ; ( iii ) x − 1, y − 1, z ; ( iv ) x − 1, y , z . Characterization of nanoparticle (1′) The experimental XRD pattern of ( 1′ ), produced using the sonochemical method, is shown in Fig. 4 a. Figure 4 b presents the simulated XRD pattern of the same compound derived from single-crystal X-ray data ( 1 ). The simulated and experimental patterns demonstrated satisfactory agreement, with only slight variations in the 2 θ values. This suggests that nanoparticle obtained via sonochemical synthesis ( 1′ ) are identical to those produced via the solvothermal method. The divergence between the powder X-ray diffraction pattern and those derived from single-crystal X-ray analysis highlighted the broadening of peaks, suggesting that the particles were in the sub-micrometer dimension. The diffraction angles for both forms are 5.1°, 10.1°, and 15.1°, corresponding to the 2D crystallographic planes (002), (004), and (006), respectively. These planes confirm that ( 1′ ) exhibits a nanosheet structure [ 52 ]. Figure 4 c illustrates these crystallographic planes, with distances of 8.65 Å between (002) and (004) and 2.88 Å between (004) and (006). The diffraction angles of 19.1° and 28° correspond to planes (012) and (115), with the angle between them measuring 38.9°. The FT-IR spectrum of ( 1′ ) shows the peaks in the range of 2910–3250 cm − 1 correspond to the O–H bond stretching vibrations (Fig. S1 ). The signal at 2825 cm − 1 indicates the vibrations of the C–H bonds in the aromatic groups. Furthermore, peaks at 1754 and 1249 cm − 1 , respectively, indicated carboxyl C = O and C–O stretching vibrations. Moreover, the signal at 1530 cm − 1 indicates that C = C bonds are present in the aromatic structures. The presence of phosphate groups is confirmed by a high peak in the 1000–1100 cm − 1 range, which shows the presence of P = O and P − O stretching vibrations [ 53 ]. Lastly, twisting modes of the aromatic ring and phosphate, together with bending vibrations of P − OH and C − H, are seen below 900 cm − 1 , which is in line with observations in the literature [ 54 ]. SEM images were obtained to characterize the micromorphology of ( 1′ ). As shown in Fig. 5 a, compound ( 1′ ) exhibited uniform particles with spherical morphology and particle sizes ranging from 100 nm to 5 µm. To investigate the presence of expected elements within the material structure, researchers conducted energy dispersive X-ray (EDX) analysis and obtained mapping spectra of ( 1′ ). The EDX spectrum reveals the presence of P, O, Cu, and C in the sample, confirming the successful synthesis of ( 1′ ) (Fig. 5 b). Furthermore, elemental mapping demonstrated the well-distributed, uniform, and homogeneous presence of nanoparticles ( 1′ ) throughout the sample. TGA/DTA analysis of ( 1′ ) was performed to investigate the stability and thermal degradation characteristics of the material (Fig. S2). An initial weight loss of 5% (calculated 5.7%) was recorded in the temperature range of 50 to 150°C, which ascribed to the elimination of non-coordinated water molecules [ 55 ]. A significant weight loss of 6.0% (calculated 5.7%) occurs between 150–250°C, attributed to the release of coordinated water component. Between 250 and 350°C, a more significant weight loss (Exp. ≈ 22%, Cal. ≈ 20%) was observed, indicating the decomposition of carboxylic groups of the benzoic acid and one oxygen atom of phosphate component. Between 3500 and 500°C, the compound stabilizes at approximately 60% weight retention, indicating the formation of the residue (C₇H₇CuO₃P). Ultimately, above 500°C, the TGA curve shows a gradual weight loss, which is attributed to decomposition of organic ligand and the formation of copper oxides, which are relatively stable at higher temperatures [ 56 , 57 ]. This data underscores the thermal stability and degradation mechanisms relevant to the compound, providing insights into its thermal properties and potential applications in thermally sensitive environments. According to the IUPAC classification [ 58 ], compound ( 1′ ) exhibited a type II curve with a prominent H3 hysteresis loop in its nitrogen adsorption/desorption isotherms. The calculations revealed that the material had a BET specific surface area of approximately 19.9 m 2 /g and a total pore volume of 0.06 cm 3 /g (Fig. 6 ). Furthermore, the Barrett-Joyner-Halenda (BJH) pore size distribution analysis indicated a mesoporous structure, with an average pore diameter of approximately 12.9 nm. Catalytic studies of compound (1′) in the synthesis of THBPs The optimal conditions were investigated by assessing various parameters at 35°C, including the choice of solvent, amount of the catalyst, and reaction duration (Table 2 , entrance 1–14). In the absence of nanocatalyst ( 1′ ), no product was obtained after 120 min, indicating the importance of the presence of a catalyst in this reaction (Table 2 , entries 1 and 2). Next, the effects of various solvents and reaction times were investigated. Interestingly, a moderate yield was obtained in EtOH, toluene, solvent-free and H 2 O (Table 2 , entries 3–6). Notably, the ratio of the water-ethanol mixtures had a significant effect on the reaction progress (Table 2 , entries 7–11). Subsequently, the effect of increasing the catalyst loading was investigated. Importantly, the conversion increased with increasing catalyst loading, and the best result was observed using the catalyst (0.06 g) (Table 2 , entries 11–14). As shown in Table 2 , among the studied solvents, the water/ethanol mixture (1:1) demonstrates the best performance and provides the highest yield compared to water, ethanol, toluene, and solvent-free conditions. In this solvent, reducing the reaction time from 60 to 25 minutes results in a 95% yield, which is comparable to that achieved with longer reaction times. The optimal amount of catalyst is 0.06 g, as reducing it to 0.04 g or 0.02 g decreases the yield, while increasing it to 0.1 g does not affect the yield. Therefore, the best conditions for synthesis involve using 0.06 g of ( 1′ ) in a water/ethanol (1:1) solvent with a reaction time of 25 minutes, achieving a maximum yield of 95%. According to optimal conditions, condensation of different benzaldehyde derivatives has been investigated and the results of these studies are presented in Table 3 . The benzaldehydes with electron donating and electron withdrawing groups converted to relatively THBP products at relatively short times with very good efficiencies (Table 3 , entries 2–6). The benzaldehydes with electron donating groups (Table 3 , entries 2, 3, 5) were converted into THBP products at shorter times and higher yields in comparison to the benzaldehyde, although the benzaldehydes with electron withdrawing groups converted at longer times and lower yields. Also, the benzaldehyde derivative with the meta position compared to para position has a longer reaction time and less yield (Table 3 , entries 2, 5). However, good yield of products was achieved under mild conditions, which required only moderate temperature and green solvents. The reactions were carried out quickly, and the substrates had to be completely converted in a comparatively short time. This highlights the broad applicability of the catalyst in the synthesis of THBP derivatives, demonstrating its versatility and potential for wider application in organic synthesis. The remarkable catalytic efficiency inspired us to investigate the critical aspects of the longevity of MOF catalysts. The recoverability and reusability of the designed heterogeneous catalyst were investigated in the reaction under optimized conditions (Fig. 7 ). The heterogeneous catalyst was used with excellent yields up to seven times, with a slight reduction in the synthesis of THBP. The recyclability results of catalyst ( 1′ ) showed that the synthesis yield remained relatively constant (approximately 90 to 95%) in the initial cycles (1–4), but gradually decreased with repeated use, reaching 85% in the 7th cycle. This decrease can be attributed to the washing away of active sites or the accumulation of the byproducts [ 62 ]. Therefore, it can be concluded that the catalyst should be regenerated after four uses to achieve maximum efficiency. Finally, in order to compare the efficiency and to demonstrate the importance of the proposed method, some of the reported cases in various literature, have been gathered in Table 4 . Nanocatalyst ( 1′ ), with its simple and rapid single-step synthesis, exhibits high recyclability and efficiently facilitates the synthetic reaction of (THBPs) in green solvents. By achieving high efficiency at optimal temperature and time, this catalyst offers significant potential for advancing sustainable practices in organic synthesis. Table 4 The comparison of the conditions and the results of reported works with compound ( 1′ ) Entry Conditions Time (min) Yield (%) Ref. 1 CaHPO 4 , H 2 O/EtOH (4:1), 80°C 120 92 [ 63 ] 2 Fe 3 -xTixO 4 @SO 3 HNPs, H 2 O/EtOH (1:1), reflux 60 95 [ 64 ] 3 2-aminopyridine, EtOH, reflux 8 91 [ 65 ] 4 DABCO-IL, H 2 O, 75°C 720 90 [ 66 ] 5 H 2 PO 4 -SCMNPs, solvent‐free, 80°C 20 92 [ 36 ] 6 GO–Si–NH 2 –PMo, Solvent-free, 90°C 300 94 [ 67 ] 7 Fe 3 O 4 @SiO 2 -NH 2 /GO/IL-Mn, H 2 O, rt 40 95 [ 68 ] 8 CaO@SiO 2 -SO 3 H, H 2 O, 50°C 20 93 [ 69 ] 9 Cu-MPMB, H 2 O/EtOH (1:1), 35ºC 25 95 This Work Figure 8 depicts a feasible pathway for THBP synthesis using catalyst ( 1′ ). The process begins with adsorption of aldehyde and malononitrile compounds by hydrogen bindings on carboxyl group of catalyst ( 1′ ), which amplifies the electrophilic properties of both the aldehyde’s carbonyl group and malononitrile. This is followed by a Knoevenagel condensation reaction between activated malononitrile and activated aldehyde. The subsequent dehydration step leads to the formation of the 2-benzylidenemalononitrile intermediate (I). In continuous, the addition of enolizable dimedone to the 2-benzylidenemalononitrile intermediate (II), followed by continuous intramolecular cyclization, gives intermediate (III). Finally, tautomerization yielded the corresponding THBP (IV) [ 70 ]. Conclusion In this work, a novel Cu(II) organic framework [Cu(H 2 O)( m -PO 3 CH 2 C 6 H 4 CO 2 H)] n ( 1 ) was synthesized using two different methods and characterized by some techniques. The crystal structure of ( 1 ) was a 2D MOF and revealed that the coordination number of the Cu(II) ion is six. The nanocatalyst ( 1 ′) offers great potential for efficient and eco-friendly synthesis of tetrahydrobenzo[b]pyrans (THBPs) through multicomponent reactions (MCRs). The best conditions for THBP synthesis were determined based on solvent selection, catalyst loading, and duration. Again, it's mentioned within the research that the catalyst was strong in performance in different aldehyde substrates at mild reaction conditions. Furthermore, recyclability studies showed up to seven cycles of reusing nanocatalyst ( 1 ′) with a gradual decline in yield only as being shown compared to previously reported catalytic systems. The findings essentially show that the catalyst could have been better than alternative catalysts. However, this study indicates the required dedication to making further advances in developing catalytic regeneration technologies to ensure efficient use over an extended period. Declarations Acknowledgments The authors are grateful to the Persian Gulf University of I.R. Iran, for this research. Author contributions E. J. B., Methodology, data collection, writing-original draft preparation, Kh. M. , Supervisor, Conceptualization, Writing-original draft preparation, P. H., Writing-review and editing, J. J ., Writing-review and editing and Software. Competing interests The author(s) declare that there are no competing interests regarding the publication of this article. Supporting Information Additional materials contain table and figures related to this work. CCDC no. 2434751 contains the supplementary crystallographic data for . These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected] . Data Availability The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request. References Jiao, L., Wang, Y., Jiang, H. L. & Xu, Q. Metal–organic frameworks as platforms for catalytic applications. Adv. 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Ataie, F., Abolghasem, D., Khojastehnezhad, A. & and Graphene oxide functionalized organic-inorganic hybrid (GO–Si–NH 2 –PMo): an efficient and green catalyst for the synthesis of tetrahydrobenzo[b]pyran derivatives. Polycycl. Aromat. Compd. 41 , 781–794. https://doi.org/10.1080/10406638.2019.1622137 (2021). Dadvar, F. & Elhamifar, D. Magnetic silica/graphene oxide nanocomposite supported ionic liquid–manganese complex as a powerful catalyst for the synthesis of tetrahydrobenzopyrans. Sci. Rep. 13 , 19354. https://doi.org/10.1038/s41598-023-46629-4 (2023). Sameri, F., Mobinikhaledi, A. & Bodaghifard, M. A. Preparation of core/shell CaO@SiO 2 -SO 3 H as a novel and recyclable nanocatalyst for one-pot synthesize of dihydropyrano[2,3-c]pyrazoles and tetrahydrobenzo[b]pyrans. Silicon 14 , 1395–1406. https://doi.org/10.1007/s12633-021-00942-7 (2022). Faroughi Niya, H., Hazeri, N., Rezaie Kahkhaie, M. & Maghsoodlou, M. T. Preparation and characterization of MNPs–PhSO 3 H as a heterogeneous catalyst for the synthesis of benzo[b]pyran and pyrano[3,2-c]chromenes. Res. Chem. Intermed . 46 , 1685–1704. https://doi.org/10.1007/s11164-019-04056-z (2020). Tables Tables 2 and 3 are available in the Supplementary Files section. Additional Declarations No competing interests reported. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6330783","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":440087798,"identity":"e20ff7fb-a096-49c2-bc7c-d2149bde7f9f","order_by":0,"name":"Ehsan Joukar Bahaderani","email":"","orcid":"","institution":"Persian Gulf University","correspondingAuthor":false,"prefix":"","firstName":"Ehsan","middleName":"Joukar","lastName":"Bahaderani","suffix":""},{"id":440087799,"identity":"b7448497-a27c-4374-a3cf-def753f7bfb1","order_by":1,"name":"Khosro Mohammadi","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA6UlEQVRIiWNgGAWjYBACCQkGBmYIM7HxAUz0ALFamg1I1ZLAJkGUwyRndyc+LqjZFs3fntxWXfDrMAN/+wHGwxV4tEjLnN1sPOPY7dwZZx623Z7Zd5hB4kwCw8EzeLTISeRuk+Zhu53bcCOx7TZvz2EGhhsMDAcbCGr5dzt3PlBLMUiLPCEt0iAtvG23czcAtTDz/DjMYEBIi+SM3M3GvH23czeeedgsPbMhncfwTGIDXi0SN3I3Pub5djt33vH0h58L/ljLyR0/fPgjPi0ogJmxjYGHgYGRaA2gOP1DvOJRMApGwSgYOQAAfRhXDkEYnu4AAAAASUVORK5CYII=","orcid":"","institution":"Persian Gulf University","correspondingAuthor":true,"prefix":"","firstName":"Khosro","middleName":"","lastName":"Mohammadi","suffix":""},{"id":440087800,"identity":"c9db11f9-76b8-402a-9330-67ece94426fb","order_by":2,"name":"Payam Hayati","email":"","orcid":"","institution":"University of Insubria","correspondingAuthor":false,"prefix":"","firstName":"Payam","middleName":"","lastName":"Hayati","suffix":""},{"id":440087801,"identity":"d3401602-2517-4f5e-a522-79490ebfb005","order_by":3,"name":"Jan Janczak","email":"","orcid":"","institution":"Polish Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Jan","middleName":"","lastName":"Janczak","suffix":""}],"badges":[],"createdAt":"2025-03-28 21:08:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6330783/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6330783/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-14653-1","type":"published","date":"2025-10-03T15:57:17+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":80223188,"identity":"8c2c480a-d8a8-4bda-9aef-9ed56c54550b","added_by":"auto","created_at":"2025-04-09 11:15:45","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":185132,"visible":true,"origin":"","legend":"\u003cp\u003eThe\u003cstrong\u003e \u003c/strong\u003eSynthetic routes of compounds (\u003cstrong\u003e1\u003c/strong\u003e) and (\u003cstrong\u003e1ʹ\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/673b0c66cfc749c51401688d.png"},{"id":80223190,"identity":"e200ac8f-68a6-4058-bc19-4addb623f868","added_by":"auto","created_at":"2025-04-09 11:15:45","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":139041,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea) \u003c/strong\u003eORTEP representation of the asymmetric unit and \u003cstrong\u003eb\u003c/strong\u003e) Coordination modes of the MPMB linker in (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/7bba769c7f7c9679f0b48e35.png"},{"id":80222234,"identity":"555b00a6-0eb5-4313-8082-3221185b64e4","added_by":"auto","created_at":"2025-04-09 11:07:46","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":311005,"visible":true,"origin":"","legend":"\u003cp\u003eThe inter and intramolecular interactions in compound \u003cstrong\u003e(1). (a\u003c/strong\u003e) The covalence and (\u003cstrong\u003eb\u003c/strong\u003e) the hydrogen bonding.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/681c5f045c7af2e4f80a9d46.png"},{"id":80223185,"identity":"f99ed33b-2153-42a0-aa0f-785882540af2","added_by":"auto","created_at":"2025-04-09 11:15:45","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":116032,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns: (\u003cstrong\u003ea\u003c/strong\u003e) nanostructure (\u003cstrong\u003e1′\u003c/strong\u003e), (\u003cstrong\u003eb\u003c/strong\u003e) single crystal (\u003cstrong\u003e1\u003c/strong\u003e), and (\u003cstrong\u003ec\u003c/strong\u003e) simulated lattice planes in crystal.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/2acad9ce1eb8dc8b0ab26fb2.png"},{"id":80222235,"identity":"1de7650d-d475-40e4-857b-40684eb94aee","added_by":"auto","created_at":"2025-04-09 11:07:46","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":445639,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003e) SEM image, \u003cstrong\u003eb\u003c/strong\u003e) EDX analysis and mapping of nanoparticles (\u003cstrong\u003e1′\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/b8152a17ca2253f82f74d27b.png"},{"id":80224105,"identity":"91badd70-39c4-44ec-b275-1f23b61eff33","added_by":"auto","created_at":"2025-04-09 11:23:45","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":56949,"visible":true,"origin":"","legend":"\u003cp\u003eNitrogen adsorption–desorption of compound (\u003cstrong\u003e1′\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/16a4eceb3f6b1150688cd503.png"},{"id":80224106,"identity":"1cfb8748-62f9-4e00-b042-d092f4f7adce","added_by":"auto","created_at":"2025-04-09 11:23:45","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":14779,"visible":true,"origin":"","legend":"\u003cp\u003eRecycling and reusability of compound (\u003cstrong\u003e1′\u003c/strong\u003e)\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/fe1765b8d86cf30cd8f97cd3.png"},{"id":80222219,"identity":"88238457-1fca-4216-b711-626aa9dfa00a","added_by":"auto","created_at":"2025-04-09 11:07:45","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":88161,"visible":true,"origin":"","legend":"\u003cp\u003eThe proposed mechanism for the synthesis of THBPs using nanocatalyst (\u003cstrong\u003e1′\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/acdea85ec478475484747684.png"},{"id":92883713,"identity":"eecf0223-a7b3-40c6-996f-92eaec9e2174","added_by":"auto","created_at":"2025-10-06 16:08:26","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2174600,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/0c3e0792-6950-425f-b13d-d204fd1ade01.pdf"},{"id":80223186,"identity":"4f28df30-55d2-4e4f-83a5-681fd307cdbb","added_by":"auto","created_at":"2025-04-09 11:15:45","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":318760,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformationJMSR.docx","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/9b894c01b14b292cffda539f.docx"},{"id":80223213,"identity":"03cdf346-0d4b-4272-a897-e7c90fb689b4","added_by":"auto","created_at":"2025-04-09 11:15:47","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":94241,"visible":true,"origin":"","legend":"","description":"","filename":"Table2and3.docx","url":"https://assets-eu.researchsquare.com/files/rs-6330783/v1/55ebad9266c0d7629bf46ace.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Design and catalytic performance of a novel 2D copper MOF for green synthesis of tetrahydrobenzo[b]pyrans","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe growing demand for efficient and environmentally benign catalytic systems for organic synthesis has attracted significant research interest in metal-organic frameworks (MOFs) as catalysts [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. These materials, characterized by metal ions coordinated to organic ligands, offer unique structural properties, such as tunable porosity, high surface area, and the ability to incorporate various functionalities into their frameworks [\u003cspan additionalcitationids=\"CR5 CR6\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. MOFs have demonstrated considerable potential as heterogeneous catalysts, effectively facilitating a range of chemical transformations owing to their intrinsic properties, including the diffusion of reactants and stabilization of transition states [\u003cspan additionalcitationids=\"CR9 CR10\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTwo-dimensional (2D) MOFs offer significant advantages over traditional three-dimensional (3D) MOFs by providing an increased surface area and enhanced reactant accessibility [\u003cspan additionalcitationids=\"CR13 CR14\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. 2D MOFs are also better suited for film formation, making them useful for applications such as electrochemical energy storage, electrocatalysis, and photocatalysis [\u003cspan additionalcitationids=\"CR17\" citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. 2D MOFs exhibit chemical and thermal stabilities comparable to or surpassing those of their three-dimensional counterparts [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. These 2D structures have gained attention as potential replacements for costly noble metals, and are being explored for applications such as electrocatalysts and photocatalytic semiconductors [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. The advantages of zeolites were first demonstrated, paving the way for their development in heterogeneous catalysis [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe distinctive characteristics of 2D MOFs, including their high surface area, accessibility, facile separation, and environmental recoverability, make them appealing candidates for catalytic applications. Some reports on this matter include (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e[In\u003csub\u003e3\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e(BPDC)\u003csub\u003e5\u003c/sub\u003e] [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] and [Cd(PBA)(DMF)].DMF [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], Au-1@Ni-NMOF [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e], Pd/NUS-SO\u003csub\u003e3\u003c/sub\u003eH [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], MF-Cu-BDC-8 [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], Ni-BDC MOF [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], and Cu(II)\u0026ndash;5N\u003csub\u003e3\u003c/sub\u003eIP [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eUltrasonic waves in chemical synthesis improve reaction kinetics and product selectivity by causing cavitation, generating high temperatures and pressures, and promoting faster and more uniform reactant mixing [\u003cspan additionalcitationids=\"CR31 CR32\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAmong the various classes of organic compounds, tetrahydrobenzo[b]pyrans (THBPs) are particularly noteworthy because of their prevalence in pharmaceuticals, agrochemicals, and natural products [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. They exhibit diverse biological activities, including antibacterial, anticancer, and anti-inflammatory properties, making their synthesis an area of interest in medicinal chemistry [\u003cspan additionalcitationids=\"CR36\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. Traditional synthetic routes for THBPs often involve multiple steps and the use of harsh reagents, leading to low yields and the generation of hazardous waste [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. In chemistry, a significant technique known as the multicomponent reaction (MCR) involves the use of three or more starting materials to create valuable organic compounds [\u003cspan additionalcitationids=\"CR41 CR42\" citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. THBPs have been synthesized using various catalytic systems; however, most of them have unfavorable characteristics, such as excessive catalyst loading, the use of hazardous organic solvents, high reaction temperatures, and catalyst non-recoverability [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAs a result, one of the biggest challenges in this field is creating a novel and powerful catalytic mechanism to get over the aforementioned restrictions. By contributing to the understanding of catalytic pathways and the design of multifunctional materials, this study aims to support the development of greener methodologies in organic chemistry and expand the scope of MOFs for heterogeneous catalysis. This study reports the ultrasonic synthesis of a novel 2D MOF designed specifically as a heterogeneous catalyst for the efficient THBP synthesis.\u003c/p\u003e"},{"header":"Experimental section","content":"\n\u003ch3\u003eMaterials and methods\u003c/h3\u003e\n\u003cp\u003eAll the chemicals and solvents were purchased from Sigma-Aldrich and Merck and used without further purification. The spectroscopic characterization of the synthesized compounds is achieved by recording Fourier transform infrared (FT-IR) spectra using a JASCO FT/IR-4600 spectrometer. Powder X-ray diffraction (PXRD) was perform applying an X\u0026rsquo;pert diffractometer created by Philips with monochromatized Cu K\u003cem\u003eα\u003c/em\u003e radiation and scanning electron microscope (SEM) was performed using a VEGA3 microscope. Sonochemical experiments were performed using an US\u0026ndash;Scientz-750F generator. Melting points were determined using a Kr\u0026uuml;ss KSB1N-apparatus in open capillary tubes. Energy-dispersive X-ray spectroscopy (EDX) was performed using an EDAX-EDS Tescan-Vega2 instrument. Thermal gravimetric analysis (TGA) was carried out using a Perkin Elmer STA6000 apparatus. Brunauer-Emmett-Teller (BET) analysis was performed via Micromeritics Asap2020 apparatus. The SIGMA 2-16p centrifuge was effectively utilized in the process of separating catalysts from the mixtures.\u003c/p\u003e \u003cp\u003eThe intensity of single-crystal X-ray data for [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e (1) was measured using a Xcalibur four-circle κ geometry diffractometer with an Atlas two-dimensional area CCD detector at room temperature. The measurements were performed using graphite monochromatic Mo Kα radiation. Data collections, cell refinements, integration, correction for Lorenz and polarisation effects and absorption corrections were performed using the CrysAlisPro 1.171.42.93a program system [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. Using Olex2 [\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e], the structure was solved by the direct methods using SHELXT [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e] and refined with the SHELXL-2018/3 program [\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. The hydrogen atoms joined to aromatic carbon atoms were introduced in their geometrical positions and treated as rigid with U\u003csub\u003eiso\u003c/sub\u003e=1.2U\u003csub\u003eeq\u003c/sub\u003e (C). The positions of the hydrogen atoms linked to oxygen atoms were refined with U\u003csub\u003eiso\u003c/sub\u003e=1.5U\u003csub\u003eeq\u003c/sub\u003e (O). The final difference Fourier maps showed no peaks of chemical significance. Details of the data collection parameters, crystallographic data and final agreement parameters are collected in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. Diamond 3.0 program [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e] was used for visualization of the structure.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of the single crystal\u003c/b\u003e (\u003cb\u003e1\u003c/b\u003e) \u003cb\u003eand nanoparticles\u003c/b\u003e (\u003cb\u003e1\u0026prime;\u003c/b\u003e)\u003c/p\u003e \u003cp\u003e \u003cem\u003eSynthesis of [Cu(H\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eO)(m-PO\u003c/em\u003e \u003csub\u003e \u003cem\u003e3\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eCH\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eC\u003c/em\u003e \u003csub\u003e \u003cem\u003e6\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eH\u003c/em\u003e \u003csub\u003e \u003cem\u003e4\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eCO\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eH)]\u003c/em\u003e \u003csub\u003e \u003cem\u003en\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eas MOF single crystals\u003c/em\u003e (\u003cb\u003e1\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eTo synthesize crystalline [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e, CuSO\u003csub\u003e4\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO (0.1 mmol, 0.0249 g) and \u003cem\u003em\u003c/em\u003e-(phosphonomethyl)benzoic acid (MPMB) (0.1 mmol, 0.0216 g) were mixed in 10 mL of methanol and 1 mL deionized water and stirred at ambient temperature for 30 min. A Parr Teflon container was used to hold the reaction mixture, which was subsequently placed inside a stainless-steel tank. Following that, the tank was sealed in autoclave and heated to 110\u0026deg;C for a whole day. The reaction mixture was slowly cooled to room temperature, and blue-green crystals of [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e appeared and were identified using X-ray analysis.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSonochemical synthesis of [Cu(H\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eO)(m-PO\u003c/em\u003e \u003csub\u003e \u003cem\u003e3\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eCH\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eC\u003c/em\u003e \u003csub\u003e \u003cem\u003e6\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eH\u003c/em\u003e \u003csub\u003e \u003cem\u003e4\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eCO\u003c/em\u003e \u003csub\u003e \u003cem\u003e2\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eH)]\u003c/em\u003e \u003csub\u003e \u003cem\u003en\u003c/em\u003e \u003c/sub\u003e \u003cem\u003eas MOF nanostructure\u003c/em\u003e (\u003cb\u003e1\u0026prime;\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eCompound (\u003cb\u003e1\u0026prime;\u003c/b\u003e) in powder form, [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e, was synthesized by combining CuSO\u003csub\u003e4\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO (1 mmol, 0.249 g) with MPMB (1 mmol, 0.216 g) in a solution of 20 mL methanol and 2 mL deionized water. At room temperature, the mixture was stirred for half an hour. Specifically, the mixture was placed in a beaker and exposed to an ultrasonic frequency of 60 Hz for 30 min. The bath temperature was maintained at 50\u0026deg;C during the entire irradiation period. Following sonication, a light blue-green powder precipitate was observed, indicating the formation of the desired product. The solid was isolated via filtration and subsequently purified by washing with methanol, followed by copious amounts of deionized water. The resulting light-blue-green powder was characterized using appropriate analytical techniques to confirm its identity.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of THBPs using nanocatalyst\u003c/b\u003e (\u003cb\u003e1\u0026prime;\u003c/b\u003e)\u003c/p\u003e \u003cp\u003eThis was accomplished by mixing nanocatalyst (\u003cb\u003e1\u0026prime;\u003c/b\u003e) (0.06 g) with distilled water and ethanol in a 1:1 ratio (5 mL/5 mL), along with benzaldehyde (1 mmol), malononitrile (1.2 mmol), and dimedone (1 mmol). The resulting solution was then agitated vigorously at 35\u0026deg;C. The reaction\u0026rsquo;s development was tracked using thin-layer chromatography (TLC). After completing the reaction, catalyst (\u003cb\u003e1\u0026prime;\u003c/b\u003e) was removed by centrifugation, and then hot ethanol was added. The final solution was placed in an ice bath to facilitate the crystallization or precipitation of the desired pure products.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n \u003ch2\u003eSynthetic perspective\u003c/h2\u003e\n \u003cp\u003eMPMB and copper(II) sulfate pentahydrate were combined in a methanol/water solvent combination to create the two-dimensional coordination complex [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e. The solvothermal technique was employed to grow single crystals of the new MOF, which were suitable for X-ray crystallographic analysis. Meanwhile, compound (\u003cstrong\u003e1ʹ\u003c/strong\u003e) was obtained by reacting MPMB and copper(II) sulfate pentahydrate in a 1:1 stoichiometric ratio in methanol/water, with ultrasonic assistance, as illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eX-ray single crystal structure\u003c/h3\u003e\n\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\n \u003ch2\u003eCrystal structure description\u003c/h2\u003e\n \u003cp\u003eThe monoclinic centrosymmetric space group P2\u003csub\u003e1\u003c/sub\u003e/n was the crystallization structure for, as shown in Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e. The ORTEP view of (\u003cstrong\u003e1\u003c/strong\u003e) is depicted in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. Compound (\u003cstrong\u003e1\u003c/strong\u003e) exhibited a unit cell volume of 943.099 \u0026Aring;\u003csup\u003e3\u003c/sup\u003e. Examination of the inorganic layer revealed that Cu\u003csup\u003e2+\u003c/sup\u003e ions establish connections with the oxygen atoms of the phosphonate groups (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e). Water molecules were added to complete the coordination polyhedron surrounding the copper atoms, resulting in an octahedral arrangement of the oxygen atoms. The octahedron exhibited an irregular shape, with five of its bonds measuring between 1.938(4) \u0026Aring; and 2.231(4) \u0026Aring;, whereas one bond was significantly elongated at 2.581(4) \u0026Aring;. The tetrahedral structure surrounding each phosphorus atom consists of three oxygen atoms and one carbon atom. Each octahedron is connected at its corners to four adjacent octahedra, forming a structure resembling a perovskite layer. In the structure, the PO\u003csub\u003e3\u003c/sub\u003eC tetrahedra are connected to the CuO\u003csub\u003e6\u003c/sub\u003e octahedra by sharing one edge, forming the CuPO\u003csub\u003e7\u003c/sub\u003eC groups. These groups bear resemblance to the VPO\u003csub\u003e8\u003c/sub\u003e units found in Li\u003csub\u003e2\u003c/sub\u003eVO\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e frameworks [\u003cspan class=\"CitationRef\"\u003e50\u003c/span\u003e] and layered M(II)(RPO\u003csub\u003e3\u003c/sub\u003e).H\u003csub\u003e2\u003c/sub\u003eO [\u003cspan class=\"CitationRef\"\u003e51\u003c/span\u003e]. Furthermore, the PO\u003csub\u003e3\u003c/sub\u003eC tetrahedra shared a single corner with an additional octahedron. The perovskite layer undergoes significant deformation owing to this bonding, causing the octahedra to tilt dramatically in relation to the plane containing Cu\u003csup\u003e2+\u003c/sup\u003e ions.\u003c/p\u003e\n \u003cp\u003eCompound (\u003cstrong\u003e1\u003c/strong\u003e) showcases a sturdy molecular framework. The structure is composed of alternating layers of inorganic and organic materials arranged in a systematic pattern (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e). The copper ion and ligand units of molecules covalently attached to others in a 2D structure (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea). Also, Hydrogen bonding interactions are notable within the 3D structure. The organic section exhibited supramolecular dimeric entities characterized by pairs of carboxylic acid groups (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb). The O1‧‧‧O2 interaction has a distance of 2.614(8) \u0026Aring;, whereas the O2\u0026ndash;H21‧‧‧ O1\u003csup\u003e\u003cem\u003ei\u003c/em\u003e\u003c/sup\u003e bond forms an angle of 161\u0026deg;. Beyond the aforementioned supramolecular interactions, Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e details the hydrogen bonding involving water molecules coordinated to the copper atom.\u0026nbsp;\u003c/p\u003e\n \u003ctable id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eHydrogen-bond data (\u0026Aring;, \u0026ordm;) in (\u003cstrong\u003e1\u003c/strong\u003e).\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eD\u003c/em\u003e\u0026mdash;H\u0026middot;\u0026middot;\u0026middot;\u003cem\u003eA\u003c/em\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eD\u003c/em\u003e\u0026mdash;H\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eH\u0026middot;\u0026middot;\u0026middot;\u003cem\u003eA\u003c/em\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eD\u003c/em\u003e\u0026middot;\u0026middot;\u0026middot;\u003cem\u003eA\u003c/em\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eD\u003c/em\u003e\u0026mdash;H\u0026middot;\u0026middot;\u0026middot;\u003cem\u003eA\u003c/em\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2\u0026mdash;H21\u0026middot;\u0026middot;\u0026middot;O1\u003csup\u003e\u003cem\u003ei\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.82\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.82\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.614 (8)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e161\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO6\u0026mdash;H61\u0026middot;\u0026middot;\u0026middot;O3\u003csup\u003e\u003cem\u003eii\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.901 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e146\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO6\u0026mdash;H61\u0026middot;\u0026middot;\u0026middot;O5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.31\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.908 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e124\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO6\u0026mdash;H62\u0026middot;\u0026middot;\u0026middot;O4\u003csup\u003e\u003cem\u003eiii\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.068 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e161\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO6\u0026mdash;H62\u0026middot;\u0026middot;\u0026middot;O5\u003csup\u003e\u003cem\u003eiv\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.36\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.905 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e119\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003eSymmetry codes: (\u003cem\u003ei\u003c/em\u003e)\u0026thinsp;\u0026minus;\u0026thinsp;\u003cem\u003ex\u003c/em\u003e\u0026thinsp;+\u0026thinsp;1, \u0026minus;\u003cem\u003ey\u003c/em\u003e, \u0026minus;\u003cem\u003ez\u003c/em\u003e\u0026thinsp;+\u0026thinsp;1; (\u003cem\u003eii\u003c/em\u003e) \u003cem\u003ex\u003c/em\u003e, \u003cem\u003ey\u003c/em\u003e\u0026thinsp;\u0026minus;\u0026thinsp;1, \u003cem\u003ez\u003c/em\u003e; (\u003cem\u003eiii\u003c/em\u003e) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;\u0026minus;\u0026thinsp;1, \u003cem\u003ey\u003c/em\u003e\u0026thinsp;\u0026minus;\u0026thinsp;1, \u003cem\u003ez\u003c/em\u003e; (\u003cem\u003eiv\u003c/em\u003e) \u003cem\u003ex\u003c/em\u003e\u0026thinsp;\u0026minus;\u0026thinsp;1, \u003cem\u003ey\u003c/em\u003e, \u003cem\u003ez\u003c/em\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eCharacterization of nanoparticle (1\u0026prime;)\u003c/h2\u003e\n \u003cp\u003eThe experimental XRD pattern of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e), produced using the sonochemical method, is shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea. Figure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb presents the simulated XRD pattern of the same compound derived from single-crystal X-ray data (\u003cstrong\u003e1\u003c/strong\u003e). The simulated and experimental patterns demonstrated satisfactory agreement, with only slight variations in the 2\u003cem\u003e\u0026theta;\u003c/em\u003e values. This suggests that nanoparticle obtained via sonochemical synthesis (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) are identical to those produced via the solvothermal method. The divergence between the powder X-ray diffraction pattern and those derived from single-crystal X-ray analysis highlighted the broadening of peaks, suggesting that the particles were in the sub-micrometer dimension. The diffraction angles for both forms are 5.1\u0026deg;, 10.1\u0026deg;, and 15.1\u0026deg;, corresponding to the 2D crystallographic planes (002), (004), and (006), respectively. These planes confirm that (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) exhibits a nanosheet structure [\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e]. Figure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec illustrates these crystallographic planes, with distances of 8.65 \u0026Aring; between (002) and (004) and 2.88 \u0026Aring; between (004) and (006). The diffraction angles of 19.1\u0026deg; and 28\u0026deg; correspond to planes (012) and (115), with the angle between them measuring 38.9\u0026deg;.\u003c/p\u003e\n \u003cp\u003eThe FT-IR spectrum of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) shows the peaks in the range of 2910\u0026ndash;3250 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to the O\u0026ndash;H bond stretching vibrations (Fig. \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e). The signal at 2825 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e indicates the vibrations of the C\u0026ndash;H bonds in the aromatic groups. Furthermore, peaks at 1754 and 1249 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, indicated carboxyl C\u0026thinsp;=\u0026thinsp;O and C\u0026ndash;O stretching vibrations. Moreover, the signal at 1530 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e indicates that C\u0026thinsp;=\u0026thinsp;C bonds are present in the aromatic structures. The presence of phosphate groups is confirmed by a high peak in the 1000\u0026ndash;1100 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e range, which shows the presence of P\u0026thinsp;=\u0026thinsp;O and P\u0026thinsp;\u0026minus;\u0026thinsp;O stretching vibrations [\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e]. Lastly, twisting modes of the aromatic ring and phosphate, together with bending vibrations of P\u0026thinsp;\u0026minus;\u0026thinsp;OH and C\u0026thinsp;\u0026minus;\u0026thinsp;H, are seen below 900 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which is in line with observations in the literature [\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e].\u003c/p\u003e\n \u003cp\u003eSEM images were obtained to characterize the micromorphology of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e). As shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea, compound (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) exhibited uniform particles with spherical morphology and particle sizes ranging from 100 nm to 5 \u0026micro;m. To investigate the presence of expected elements within the material structure, researchers conducted energy dispersive X-ray (EDX) analysis and obtained mapping spectra of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e). The EDX spectrum reveals the presence of P, O, Cu, and C in the sample, confirming the successful synthesis of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eb). Furthermore, elemental mapping demonstrated the well-distributed, uniform, and homogeneous presence of nanoparticles (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) throughout the sample.\u003c/p\u003e\n \u003cp\u003eTGA/DTA analysis of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) was performed to investigate the stability and thermal degradation characteristics of the material (Fig. S2). An initial weight loss of 5% (calculated 5.7%) was recorded in the temperature range of 50 to 150\u0026deg;C, which ascribed to the elimination of non-coordinated water molecules [\u003cspan class=\"CitationRef\"\u003e55\u003c/span\u003e]. A significant weight loss of 6.0% (calculated 5.7%) occurs between 150\u0026ndash;250\u0026deg;C, attributed to the release of coordinated water component. Between 250 and 350\u0026deg;C, a more significant weight loss (Exp. \u0026asymp; 22%, Cal. \u0026asymp; 20%) was observed, indicating the decomposition of carboxylic groups of the benzoic acid and one oxygen atom of phosphate component. Between 3500 and 500\u0026deg;C, the compound stabilizes at approximately 60% weight retention, indicating the formation of the residue (C₇H₇CuO₃P). Ultimately, above 500\u0026deg;C, the TGA curve shows a gradual weight loss, which is attributed to decomposition of organic ligand and the formation of copper oxides, which are relatively stable at higher temperatures [\u003cspan class=\"CitationRef\"\u003e56\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e57\u003c/span\u003e]. This data underscores the thermal stability and degradation mechanisms relevant to the compound, providing insights into its thermal properties and potential applications in thermally sensitive environments.\u003c/p\u003e\n \u003cp\u003eAccording to the IUPAC classification [\u003cspan class=\"CitationRef\"\u003e58\u003c/span\u003e], compound (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) exhibited a type II curve with a prominent H3 hysteresis loop in its nitrogen adsorption/desorption isotherms. The calculations revealed that the material had a BET specific surface area of approximately 19.9 m\u003csup\u003e2\u003c/sup\u003e/g and a total pore volume of 0.06 cm\u003csup\u003e3\u003c/sup\u003e/g (Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e). Furthermore, the Barrett-Joyner-Halenda (BJH) pore size distribution analysis indicated a mesoporous structure, with an average pore diameter of approximately 12.9 nm.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eCatalytic studies of compound (1\u0026prime;) in the synthesis of THBPs\u003c/h3\u003e\n\u003cp\u003eThe optimal conditions were investigated by assessing various parameters at 35\u0026deg;C, including the choice of solvent, amount of the catalyst, and reaction duration (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, entrance 1\u0026ndash;14). In the absence of nanocatalyst (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e), no product was obtained after 120 min, indicating the importance of the presence of a catalyst in this reaction (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, entries 1 and 2). Next, the effects of various solvents and reaction times were investigated. Interestingly, a moderate yield was obtained in EtOH, toluene, solvent-free and H\u003csub\u003e2\u003c/sub\u003eO (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, entries 3\u0026ndash;6). Notably, the ratio of the water-ethanol mixtures had a significant effect on the reaction progress (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, entries 7\u0026ndash;11). Subsequently, the effect of increasing the catalyst loading was investigated. Importantly, the conversion increased with increasing catalyst loading, and the best result was observed using the catalyst (0.06 g) (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, entries 11\u0026ndash;14).\u003c/p\u003e\n\u003cp\u003eAs shown in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e, among the studied solvents, the water/ethanol mixture (1:1) demonstrates the best performance and provides the highest yield compared to water, ethanol, toluene, and solvent-free conditions. In this solvent, reducing the reaction time from 60 to 25 minutes results in a 95% yield, which is comparable to that achieved with longer reaction times. The optimal amount of catalyst is 0.06 g, as reducing it to 0.04 g or 0.02 g decreases the yield, while increasing it to 0.1 g does not affect the yield. Therefore, the best conditions for synthesis involve using 0.06 g of (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) in a water/ethanol (1:1) solvent with a reaction time of 25 minutes, achieving a maximum yield of 95%.\u003c/p\u003e\n\u003cp\u003eAccording to optimal conditions, condensation of different benzaldehyde derivatives has been investigated and the results of these studies are presented in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. The benzaldehydes with electron donating and electron withdrawing groups converted to relatively THBP products at relatively short times with very good efficiencies (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 2\u0026ndash;6). The benzaldehydes with electron donating groups (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 2, 3, 5) were converted into THBP products at shorter times and higher yields in comparison to the benzaldehyde, although the benzaldehydes with electron withdrawing groups converted at longer times and lower yields. Also, the benzaldehyde derivative with the \u003cem\u003emeta\u003c/em\u003e position compared to \u003cem\u003epara\u003c/em\u003e position has a longer reaction time and less yield (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, entries 2, 5). However, good yield of products was achieved under mild conditions, which required only moderate temperature and green solvents. The reactions were carried out quickly, and the substrates had to be completely converted in a comparatively short time. This highlights the broad applicability of the catalyst in the synthesis of THBP derivatives, demonstrating its versatility and potential for wider application in organic synthesis.\u003c/p\u003e\n\u003cp\u003eThe remarkable catalytic efficiency inspired us to investigate the critical aspects of the longevity of MOF catalysts. The recoverability and reusability of the designed heterogeneous catalyst were investigated in the reaction under optimized conditions (Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e). The heterogeneous catalyst was used with excellent yields up to seven times, with a slight reduction in the synthesis of THBP. The recyclability results of catalyst (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e) showed that the synthesis yield remained relatively constant (approximately 90 to 95%) in the initial cycles (1\u0026ndash;4), but gradually decreased with repeated use, reaching 85% in the 7th cycle. This decrease can be attributed to the washing away of active sites or the accumulation of the byproducts [\u003cspan class=\"CitationRef\"\u003e62\u003c/span\u003e]. Therefore, it can be concluded that the catalyst should be regenerated after four uses to achieve maximum efficiency.\u003c/p\u003e\n\u003cp\u003eFinally, in order to compare the efficiency and to demonstrate the importance of the proposed method, some of the reported cases in various literature, have been gathered in Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. Nanocatalyst (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e), with its simple and rapid single-step synthesis, exhibits high recyclability and efficiently facilitates the synthetic reaction of (THBPs) in green solvents. By achieving high efficiency at optimal temperature and time, this catalyst offers significant potential for advancing sustainable practices in organic synthesis.\u0026nbsp;\u003c/p\u003e\n\u003ctable id=\"Tab4\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eThe comparison of the conditions and the results of reported works with compound (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e)\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eConditions\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTime (min)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYield (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eRef.\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCaHPO\u003csub\u003e4\u003c/sub\u003e, H\u003csub\u003e2\u003c/sub\u003eO/EtOH (4:1), 80\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e120\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e63\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003e-xTixO\u003csub\u003e4\u003c/sub\u003e@SO\u003csub\u003e3\u003c/sub\u003eHNPs, H\u003csub\u003e2\u003c/sub\u003eO/EtOH (1:1), reflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e64\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2-aminopyridine, EtOH, reflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e91\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e65\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDABCO-IL, H\u003csub\u003e2\u003c/sub\u003eO, 75\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e720\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e66\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e-SCMNPs, solvent‐free, 80\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e36\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eGO\u0026ndash;Si\u0026ndash;NH\u003csub\u003e2\u003c/sub\u003e\u0026ndash;PMo, Solvent-free, 90\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e300\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e67\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e/GO/IL-Mn, H\u003csub\u003e2\u003c/sub\u003eO, rt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e68\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCaO@SiO\u003csub\u003e2\u003c/sub\u003e-SO\u003csub\u003e3\u003c/sub\u003eH, H\u003csub\u003e2\u003c/sub\u003eO, 50\u0026deg;C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e93\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e[\u003cspan class=\"CitationRef\"\u003e69\u003c/span\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e9\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eCu-MPMB, H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO/EtOH (1:1), 35\u0026ordm;C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e\u003cstrong\u003e25\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e\u003cstrong\u003e95\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003eThis Work\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e depicts a feasible pathway for THBP synthesis using catalyst (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e). The process begins with adsorption of aldehyde and malononitrile compounds by hydrogen bindings on carboxyl group of catalyst (\u003cstrong\u003e1\u0026prime;\u003c/strong\u003e), which amplifies the electrophilic properties of both the aldehyde\u0026rsquo;s carbonyl group and malononitrile. This is followed by a Knoevenagel condensation reaction between activated malononitrile and activated aldehyde. The subsequent dehydration step leads to the formation of the 2-benzylidenemalononitrile intermediate (I). In continuous, the addition of enolizable dimedone to the 2-benzylidenemalononitrile intermediate (II), followed by continuous intramolecular cyclization, gives intermediate (III). Finally, tautomerization yielded the corresponding THBP (IV) [\u003cspan class=\"CitationRef\"\u003e70\u003c/span\u003e].\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this work, a novel Cu(II) organic framework [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e1\u003c/b\u003e) was synthesized using two different methods and characterized by some techniques. The crystal structure of (\u003cb\u003e1\u003c/b\u003e) was a 2D MOF and revealed that the coordination number of the Cu(II) ion is six. The nanocatalyst (\u003cb\u003e1\u003c/b\u003e\u0026prime;) offers great potential for efficient and eco-friendly synthesis of tetrahydrobenzo[b]pyrans (THBPs) through multicomponent reactions (MCRs). The best conditions for THBP synthesis were determined based on solvent selection, catalyst loading, and duration. Again, it's mentioned within the research that the catalyst was strong in performance in different aldehyde substrates at mild reaction conditions. Furthermore, recyclability studies showed up to seven cycles of reusing nanocatalyst (\u003cb\u003e1\u003c/b\u003e\u0026prime;) with a gradual decline in yield only as being shown compared to previously reported catalytic systems. The findings essentially show that the catalyst could have been better than alternative catalysts. However, this study indicates the required dedication to making further advances in developing catalytic regeneration technologies to ensure efficient use over an extended period.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors are grateful to the Persian Gulf University of I.R. Iran, for this research.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eE. J. B.,\u0026nbsp;\u003c/strong\u003eMethodology, data collection, writing-original draft preparation, \u003cstrong\u003eKh. M.\u003c/strong\u003e, Supervisor, Conceptualization, Writing-original draft preparation, \u003cstrong\u003eP. H.,\u0026nbsp;\u003c/strong\u003eWriting-review and editing, \u003cstrong\u003eJ. J\u003c/strong\u003e., Writing-review and editing and Software.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe author(s) declare that there are no competing interests regarding the publication of this article.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupporting Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAdditional materials contain table and figures related to this work. CCDC no. 2434751 contains the supplementary crystallographic data for . These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eJiao, L., Wang, Y., Jiang, H. L. \u0026amp; Xu, Q. Metal\u0026ndash;organic frameworks as platforms for catalytic applications. \u003cem\u003eAdv. 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Intermed\u003c/em\u003e. \u003cb\u003e46\u003c/b\u003e, 1685\u0026ndash;1704. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s11164-019-04056-z\u003c/span\u003e\u003cspan address=\"10.1007/s11164-019-04056-z\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2020).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 2 and 3 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Metal-organic framework, Copper, Phosphonocarboxylic acid, Nanocatalyst, Tetrahydrobenzo[b]pyran, Multicomponent reaction, Ultrasonic","lastPublishedDoi":"10.21203/rs.3.rs-6330783/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6330783/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study explores the development and use of a novel 2D MOF as a heterogeneous catalyst in organic synthesis. The phosphonocarboxylic acid \u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH (\u003cb\u003eL\u003c/b\u003e) has been employed in the synthesis of a metal carboxyarylphosphonate. The 2D MOF [Cu(H\u003csub\u003e2\u003c/sub\u003eO)(\u003cem\u003em\u003c/em\u003e-PO\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e1\u003c/b\u003e) was synthesized in both crystal (\u003cb\u003e1\u003c/b\u003e) and nanostructure (\u003cb\u003e1\u0026prime;\u003c/b\u003e) forms, characterized by X-ray single crystallography, SEM, TGA, FT-IR, PXRD, EDX, Mapping, and nitrogen adsorption\u0026ndash;desorption, and employed for the efficient green synthesis of tetrahydrobenzo[b]pyrans (THBPs). The crystal structure features alternating inorganic and organic layers. The organic layers have supramolecular dimers of carboxylic acid groups, two molecules bonded to two inorganic layers. THBP yield optimization conditions were determined with water/ethanol as solvents, using a catalyst loading of 0.06 g for 95% yields. The synthesized catalyst demonstrated high catalytic activity, broad applicability to various aldehyde substrates, and notable reusability, maintaining high yields for up to seven cycles after the reaction. Compared with previous catalytic systems, compound (\u003cb\u003e1\u0026prime;\u003c/b\u003e) exhibited superior efficiency and recyclability. These findings highlight the potential of this novel 2D MOF for facilitating environmentally friendly and efficient organic syntheses.\u003c/p\u003e","manuscriptTitle":"Design and catalytic performance of a novel 2D copper MOF for green synthesis of tetrahydrobenzo[b]pyrans","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-09 11:07:40","doi":"10.21203/rs.3.rs-6330783/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-04-21T06:24:30+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-19T12:16:56+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-11T17:03:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"251620514357027084789260269166467352603","date":"2025-04-10T06:39:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-10T05:56:23+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"267471376171574745284733048937653861981","date":"2025-04-10T05:23:25+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"131246249387294848435572225675297928670","date":"2025-04-09T13:39:51+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"76538255996412545823210061840677656280","date":"2025-04-08T07:23:53+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-04-08T05:43:24+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-04-07T23:10:36+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-04-07T21:05:33+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-05T08:44:41+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-03-28T21:04:06+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"cf5a0f77-da97-443b-979b-5867a5de5281","owner":[],"postedDate":"April 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":46851096,"name":"Physical sciences/Chemistry"},{"id":46851097,"name":"Physical sciences/Nanoscience and technology"}],"tags":[],"updatedAt":"2025-10-06T16:01:15+00:00","versionOfRecord":{"articleIdentity":"rs-6330783","link":"https://doi.org/10.1038/s41598-025-14653-1","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-10-03 15:57:17","publishedOnDateReadable":"October 3rd, 2025"},"versionCreatedAt":"2025-04-09 11:07:40","video":"","vorDoi":"10.1038/s41598-025-14653-1","vorDoiUrl":"https://doi.org/10.1038/s41598-025-14653-1","workflowStages":[]},"version":"v1","identity":"rs-6330783","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6330783","identity":"rs-6330783","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}