Alcohol Guest Molecule Capture in a Novel Copper (II) Hydrogen-Bonded Metal- Organic Framework (HBMOF)

Alcohol Guest Molecule Capture in a Novel Copper (II) Hydrogen-Bonded Metal- Organic Framework (HBMOF) | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Alcohol Guest Molecule Capture in a Novel Copper (II) Hydrogen-Bonded Metal- Organic Framework (HBMOF) Charles T. Gross, Christina E. Hogan, Thomas G. Johnson, Jonah D. Bruyns, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7255550/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 14 Jan, 2026 Read the published version in Journal of Chemical Crystallography → Version 1 posted 9 You are reading this latest preprint version Abstract The continuous investigation of a copper (II) component that used in developing novel hydrogen-bonded metal-organic frameworks (HBMOFs). In this investigation, the copper (II) compound is reacted with phenethylamine, resulting in a complex containing a lamellar framework, which exist as a 6-coordinate copper (II) center. The use of the phenethylamine compound will afford an extended interlayer, when compared to previous (HBMOFs). This layered framework has the ability to include a variety of guest molecules, ranging from alkyl alcohols to benzyl alcohols. The discussion of four guest included hydrogen-bonded frameworks will be discussed herein and will be compared with an empty framework: (1) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 , (2) [phenethyllammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(1-pentanol), (3) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(1-hexanol), (4) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(benzyl alcohol), (5) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(4-chlorobenzyl alcohol). Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction Our research group and many groups have previously studied the ongoing investigation of developing metal-containing hydrogen-bonded layered frameworks (HBMOFs). 1–5 Where the majority of the studies the metal centre of choice has been a late, first row transition metal because first row transition metal complexes has afforded researchers thermally stable and robust frameworks 6, 7 . These metal frameworks have the likelihood to form two distinct possibilities: a layered or pillared structure 8–11 . The layered frameworks could then be classified as a bilayer (ABA) or standard layered (AB) framework, yielding a more diverse field of hydrogen-bonded frameworks. The development and formation of hydrogen-bonded metal-organic frameworks (HBMOFs) will always be dependent on the building blocks used to construct the said HBMOFs. The common building blocks of our HBMOFs will contain a metal-organic carboxylic acid compound, which will yield the layer component, and the other component is an organic amine molecule, which is the director of the interlayer region. Hogan’s research group has shown a hydrogen-bonded framework created by Cu(PDCA) 2 (H 2 O) 2 and DL-α-methylbenzylamine has included alcohol guest molecules within a bilayer formation. Using the same framework system, Hogan has also shown that this hydrogen-bonded framework could yield a layered structure when the guest molecules were changed to pyridine-based molecules. Guest inclusion into metal-containing frameworks may possess some drawbacks or limitations. It has been widely shown that layered frameworks exhibit a close-packed nature, 7 yielding smaller channels or cavities that will afford guest inclusion. Pillared frameworks, on the other hand, will contain a more open channel 8 that would allow a greater efficiency for guest inclusion. All these layered solids are excellent candidates for host-guest chemistry (e.g. storage and separations), catalysis and photopolymerization reactions 12–26 . Our focus in this study is to identify if the interlayer molecule (the amine molecule) directs the formation of the hydrogen-bonded framework (i.e. bilayer vs. layered) and if there a correlation between the size of the interlayer molecule and its ability to include guest molecules through a non-coordinative inclusion. 2. Materials and Methods All reagents and solvents used for the synthesis were commercially available and used without further purification. Powder X-ray diffraction (PXRD) was collected using a Bruker D8 X-ray diffractometer with Cu-Kα radiation (λ = 1.54060 Å) at 40 kV, 20 mA with a scanning rate of 5°/min and a step size of 0.015°. 2.1. X-ray Crystallography The single crystal X-ray diffraction data were collected on a Bruker Photon 2 area detector diffractometer. The crystal was kept at 110 K during data collection. Using Olex2 27 , the structure was solved with the XT 28 structure solution program using Intrinsic Phasing and refined with the XL 29 refinement package using Least Squares minimisation. Crystallographic details for 1 – 5 are listed in Table 1, respectively. Full crystallographic data can be found in the supplemental information. CCDC numbers: 2386068, 2386070, 2386072, 2386074, and 2386075. 2.2. Synthesis of Crystalline Materials The crystalline materials were formed from slow evaporation after the reaction between Cu(HPDCA) 2 (H 2 O) 2 and phenethylamine, followed by the layering of the corresponding guest molecule. In efforts to afford the empty framework, the synthesis was the same as above, but the layering molecule used was decane. 3. Results and discussion In this paper, we have created novel hydrogen-bonded frameworks that can include guest molecules. We have developed four new host-guest hydrogen-bonded frameworks, listed as structures 2 – 5 and the empty framework is labelled as 1 : (1) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 , (2) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(1-pentanol), (3) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(2-hexanol), (4) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(benzyl alcohol), (5) [phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 ·(4-chlorobenzyl alcohol). The coordination of phenethylammnonium ions within the framework provides a structurally adaptable interlayer environment, facilitating the reversible accommodation of guest species. The relative amount of flexibility has shown within recent hydrogen-bonded metal-organic frameworks developed by Beatty 7 and Hogan 10 . The presented structures exhibit a layered formation (AB) where the Cu(HPDCA) 2 (H 2 O) 2 forms the lamellar portion of the layered section of the framework and the amine, phenethylamine, is used as the interlayer spacing between the layers. An interesting feature of the framework is that the Cu (II) centre is bonded in an octahedral geometry with two water ligands in the axial position. When compared back to Hogan’s previous Cu-based HBMOF there is a noticeable difference in the layer pattern formation. The use of phenethylamine has afforded an octahedral metal centre, where previously used DL-α-methylbenzylamine yielded a bilayer (ABA) framework. The new complexes presented here were synthesized using Cu (HPDCA) 2 (H 2 O) 2 and phenethylamine and the unit cell of these components can be found in Figure 1 . The crystalline frameworks are deemed isostructural with one another, where the lamellar metal-layer and the organic bilayer will remain the same in all structures. The sole difference between the individual crystal structures will be dependent on the included guest molecule within the framework. The hydrogen-bonded framework forms through proton exchange between the Cu(HPDCA) 2 (H 2 O) 2 precursor and phenethylamine. This acid-base interaction leads to the in-situ formation of phenethylammonium ions, which mediate the interlayer connectivity within the lamellar structure. The acid-base reaction scheme mentioned previously will be a consistent reaction mechanism in all reported crystal structures. 3.1. [Phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 (1) Structure 1 is a non-guest filled layered framework where the complete visualization of the hydrogen-bonded framework can be identified and viewed in Figure 2 . In structure 1 , the metal-complex still contains an octahedral geometry, and the amine molecule is located in between the adjacent layers, serving as the interlayer spacer for the framework. As previous mentioned, the layer region of the framework is formed through charge-assisted hydrogen bonding between the phenethylammonium ions and the copper-based pyridine dicarboxylate ion. The phenethylammonium ions are directed in a face-to-face fashion, due to neighbouring π×××π interactions, between the layers. This layer interaction yields the overall appearance of a closed-packed crystalline network, like Beatty and Hogan’s early work 2 , where the ability for guest insertion maybe difficult. TGA analysis from the empty framework shows a small weight loss, around 4.92%, between 125°C and 175°C, where the calculated loss for two water molecules is 5.30% with in this HBMOF. The small weight loss is in a similar agreement with the loss of two coordinated water molecules. Further reactions with linear chained alcohol and benzyl alcohol molecules will shows the framework’s ability to incorporate guest molecules. A list of selected bond distances and bond angles are presented in Table 2. Table 2 Selected Bond Lengths and Bond Angles from Framework 1 Selected Bond Lengths ( Å ) Selected Bond Angles ( ͦ ) Cu – O1 1.955 (6) N2 – Cu – N1 179.8 (3) Cu – O5 1.965 (6) O5 – Cu – O1 179.6 (3) Cu – N1 2.012 (7) O1 – Cu – N1 96.2 (3) Cu – N2 2.004 (7) O5 – Cu – N2 83.4 (3) 3.2 [Phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 · 1-pentanol (2) Structure 2 is isostructural with structure 1 but contains an included 1-pentanol guest molecule. The ratio of metal ion: guest within this structure is 1:1. The host framework to guest ratio can be seen in the expanded crystal structure as shown in Figure 3 . The 1-pentanol guest molecules reside in between the layer spacers, the phenethylammonium ions, where the layer spacer exhibits the greatest disorder within this crystal structure. The major disorder within this crystal structure lies with the orientation of the -NH 3 + , where the cationic region is displaced in two positions. The extended layer formation shown is Figure 3 does not include the disordered nature of the phenethylammonium ion, simply illustrates the hydrogen-bonded directionality of the 2-D framework. As seen from the TGA plots, there were two early temperature losses, below 100°C, which has often been associated with the loss of the guest molecule and the coordinated water ligands. 3.3 [Phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 · 1-hexanol (3) Complex 3 is also isostructural with complex 1 but contains an included 1-hexanol guest molecule. Complex 3 is similar in organization to complex 2 , with respect to the location of guest molecule and the hydrogen-bonding pattern. The 1-hexanol guest molecule does not contain any disorder within its position in the crystal structure, it is noticed the 1-hexanol alternates the directionality of the hydroxyl group. The major disorder in this crystal structure is found within the phenethylammonium interlayer spacers. The ammonium head (NH 3 + ) is found in a central location, whereas the ethyl chain has rotated into a different location to yield a two-fold disorder of the phenethyl group. The hydrogen-bonded layer exhibits a slight larger spacing between neighboring Cu (PDCA) units, this is likely due to the disordered nature of the phenethylammonium cation. The crystal structure of the extended framework of complex 3 is found in Figure 4a and thermogravimetric data showing guest loss can be found in Figure 4b . The TGA data shows a weight loss occurring from 50°C to around 90°C, which corresponds to the loss of the 1-hexanol guest molecule. This initial weight loss of during this temperature range is roughly 10.3%. The theoretical occupancy for this guest-included framework is 17.6%, keeping a consistent 1:1 ratio of host framework to guest molecule. 3.4 [Phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 · benzyl alcohol (4) Complex 4 is also isostructural with complex 1 but contains an included benzyl alcohol guest molecule. Complex 4 is very similar to complex 2 , with respect to the location of guest molecule and the hydrogen-bonding pattern. The benzyl alcohol guest molecule is disordered over two positions, giving the appearance of a diol species. The benzyl alcohol molecule appears to be rotated and inverted within the channel to yield the two disordered sites. In each case, the hydroxyl group is pointing outward to a neighbouring phenethyl ammonium group. The crystal structure of the extended framework of complex 4 is found in Figure 5a and thermogravimetric data showing guest loss can be found in Figure 5b . Thermal analysis indicates desorption within the 50 - 90°C range, corroborating guest incorporation that was observed crystallographically. This initial weight loss of during this temperature range is roughly 11.7%. The theoretical occupancy for this guest-included framework is 17.6%, keeping a consistent 1:1 ratio of host framework to guest molecule. 3.5 [Phenethylammonium] 2 Cu(PDCA) 2 (H 2 O) 2 · 4-chlorobenzyl alcohol (5) Complex 5 is also isostructural with complex 1 but contains an included 4-chlorobenzyl alcohol guest molecule. Complex 5 is very similar to complex 4, with respect to the location of guest molecule and the hydrogen-bonding pattern. The 4-chlorobenzyl alcohol guest molecule is disordered over two positions, giving the appearance of a diol species. In each case the hydroxyl group is pointing outward to a neighbouring phenethyl ammonium group. The crystal structure of the extended framework of complex 5 is found in Figure 6a and thermogravimetric data showing guest loss can be found in Figure 6b . The TGA data shows a weight loss occurring from 50°C to around 90°C, which corresponds to the loss of the 4-chlorobenzyl alcohol guest molecule. This initial weight loss of during this temperature range is roughly 14.6%. The theoretical occupancy for this guest-included framework is 18.3%, keeping a consistent 1:1 ratio of host framework to guest molecule. Conclusion This study presents the successful design and synthesis of a lamellar copper (II)-based hydrogen-bonded metal-organic framework (HBMOF) capable of incorporating a diverse range of alcohol guests, from linear alkyl chains to substituted benzyl alcohols. By utilizing phenethylamine as the interlayer spacer, the resulting framework adopts a standard AB-type lamellar framework with an octahedrally coordinated Cu (II) centre. The consistent structural motif across all five complexes underscores the robustness and modularity of the framework design. The inclusion of guest molecules within the interlayer regions was confirmed through single-crystal X-ray diffraction and thermogravimetric analysis (TGA), revealing notable guest-dependent variations in structural order and thermal behavior. These findings reinforce the tunable nature of hydrogen-bonded frameworks and highlight the significance of interlayer amine selection in dictating framework topology and inclusion properties. The demonstrated host–guest versatility paves the way for future investigations into the selective sorption, separation, and functionalization capabilities of lamellar HBMOFs. Further studies will explore the role of guest polarity, molecular size, and substitution pattern on the dynamics and reversibility of inclusion processes within these adaptable frameworks. Declarations Conflicts of interest There are no conflicts to declare. Author Contribution Charles Gross, Thomas Johnson, and Jonah Bruyns contributed to the growth of the crystal and other experimental data. Christina Hogan gave analysis of data and assisted the primary PI with research development. Greg Hogan assisted in experimentations and writing of the manuscript. Acknowledgements The authors would like to express their sincere appreciation to Dr. Joseph Reibenspies from the Department of Chemistry at Texas A&M University for assistance with the x-ray crystallography. The Welch foundation’s Departmental Grant for funding, Grant No. BZ-0052-20201025 and their Instrument Grant, Grant No. Q-BZ-0022-20240404. References A. M. Beatty, Coord, Chem. Rev . 246, (2003), 131. S. A. Dalrymple, M. Parvez, G. K. Shimizu, Inorg. Chem .,41, (2002), 6986. D. Braga, Dalton , (2000), 3705. D. Braga, L. Maini, M. Polito, F. Grepioni, Struct. Bonding (Berlin), 111, (2004), 1. G. K. H. Shimzu, R. Vaidhyanathan, J. M. Taylor, Chem. Soc. Rev ., 38, (2009), 1430. A. Beatty and C. L. Chen, J. Am. Chem. Soc ., 130, (2008), 17222. A. Beatty, B. Helfrich, G. Hogan, and B. Reed, Cryst. Growth Des ., 6, (2006), 122. G. Hogan, N. Rath and A. Beatty, Cryst. Growth Des., 11, (2011), 3740. M. Fischer and A. Beatty, CrystEngComm , 16, (2014), 7313. G. J. Beach, C. E. Hogan, B. N. Besong, and G. A. Hogan , J. Mol. Struc.., 1195, (2019), 5, 744. H. H. Nguyen, C. E. Hogan, and G. A. Hogan, J. Chem. Crystallogr., 51, (2019), 82. https://doi.org/10.1007/s10870-020-00838-1. O. M. Yaghi, H. Li, C. Davis, D. Richardson and T. L. Groy, Acc. Chem. Res., 31, ( 1998) 474. A. Pivovar, K. Holman and M. Ward, Chem. Mater., 13, (2001), 3018. K. Endo, T. Koike, T. Sawaki, O. Hayashida, H. Masuda and Y. Aoyama, J. Am. Chem. Soc ., 119, (1997), 4117. R.B. Lin, Y. He, P. Li, H. Wang, W. Zhou and B. Chen, Chem. Soc. Rev ., 2019, 48, 1362-1389. M. Lu, X. Yang, Y. Li, Z. Zhu, Y. Wu, H. Xu, J. Gao and J. Yao, Chem. Asian J ., 2019,14, (9), 1590-1594. H. Cui, S. Chen, H. Arman, Y. Ye, A. Alsalme, R.B. Lin, B. Chen, Inorganica Chim. Acta , 2019, 495, 118938. K. Holman, A. Pivovar, J. Swift and M. Ward, Acc. Chem. Res ., 34, (2001), 107. A. Beatty, A. Granger, A. Simpson, Chem.-Eur. J ., 8, (2002), 3254. K. Biradha, D. Dennis, V. MacKinnon, C. Sharma, M. Zaworotko, J. Am. Chem. Soc ., 120, (1998), 11894. T. Mallouk, J. Gavin, Acc. Chem. Res ., 31, (1998), 209. S. Kitagawa, R. Kitaura, S. I. Noro, Angew. Chem., Int. Ed. , 43, (2004), 2334. M. Kang, D. W. Kang, J. H. Choe, H. Kim, D. W. Kim, H. Park and C. S. Hong, Chem. Mater. 2021, 33, 15, 6193-6199. J. Song, J. Mao, Y. Sun, H. Zeng, R. Kramer, A. Clearfield, J. Solid State Chem ., 177, (2004), 633. C. L. Chen, A. Beatty, Chem. Comm ., (2007), 76. S. Dalrymple, G. Shimizu, Chem. Comm ., (2006), 956. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Cryst., 42, (2009) 339. G. M. Sheldrick (2015). Acta Cryst. A71, 3-8. G. M. Sheldrick (2008). Acta Cryst. A64, 112-122. Table Table 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files Table1.docx Cite Share Download PDF Status: Published Journal Publication published 14 Jan, 2026 Read the published version in Journal of Chemical Crystallography → Version 1 posted Editorial decision: Revision requested 08 Sep, 2025 Reviews received at journal 02 Sep, 2025 Reviewers agreed at journal 27 Aug, 2025 Reviews received at journal 25 Aug, 2025 Reviewers agreed at journal 18 Aug, 2025 Reviewers invited by journal 12 Aug, 2025 Editor assigned by journal 08 Aug, 2025 Submission checks completed at journal 08 Aug, 2025 First submitted to journal 30 Jul, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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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-7255550","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":502095409,"identity":"e0bb911b-2e88-4ab9-96dd-c97f06a5a2ac","order_by":0,"name":"Charles T. Gross","email":"","orcid":"","institution":"Texas A\u0026M University – Texarkana","correspondingAuthor":false,"prefix":"","firstName":"Charles","middleName":"T.","lastName":"Gross","suffix":""},{"id":502095411,"identity":"e7a4428e-b646-42db-9fd5-f1f4ea512fb9","order_by":1,"name":"Christina E. 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\u003c/em\u003e\u003cstrong\u003e2 \u003c/strong\u003eshows the formation of a hydrogen-bonded layer without guest inclusion. \u0026nbsp;(b) TGA plot shows the weight loss (%) of an empty framework (green) and the derivative weight (blue).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7255550/v1/a731a4f4bedf797a6231ee53.png"},{"id":89487880,"identity":"b0d9d367-0870-4c83-94a9-df541a469b23","added_by":"auto","created_at":"2025-08-20 13:09:19","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":223838,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Crystal structure of \u003cstrong\u003e3\u003c/strong\u003e showing the extended hydrogen-bonding pattern and the included 1-hexanol molecule and (b) TGA plot shows the weight loss (%) of the guest filled framework (green).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7255550/v1/2b3cc6a31dba65494b022c8f.png"},{"id":89487897,"identity":"0a971161-7f9b-4164-8870-ea92f91101ce","added_by":"auto","created_at":"2025-08-20 13:09:23","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":258275,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Crystal structure of \u003cstrong\u003e4\u003c/strong\u003e showing the extended hydrogen-bonding pattern and the included benzyl alcohol molecule and (b) TGA plot shows the weight loss (%) of the guest filled framework (green).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7255550/v1/f40a7ddd9f3046b0be71a5b3.png"},{"id":100617374,"identity":"7585a275-d92e-4b94-baec-45131b97ffeb","added_by":"auto","created_at":"2026-01-19 17:51:46","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1563213,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7255550/v1/4e951728-e376-4207-83eb-e5f3c7f9d89d.pdf"},{"id":89487900,"identity":"c26383db-efce-40cd-b436-b1069948be9d","added_by":"auto","created_at":"2025-08-20 13:09:23","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":25971,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-7255550/v1/de4dd45f9da9dfd94bdd409e.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Alcohol Guest Molecule Capture in a Novel Copper (II) Hydrogen-Bonded Metal- Organic Framework (HBMOF)","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eOur research group and many groups have previously studied the ongoing investigation of developing metal-containing hydrogen-bonded layered frameworks (HBMOFs).\u003csup\u003e1\u0026ndash;5\u003c/sup\u003e Where the majority of the studies the metal centre of choice has been a late, first row transition metal because first row transition metal complexes has afforded researchers thermally stable and robust frameworks\u003csup\u003e6, 7\u003c/sup\u003e. These metal frameworks have the likelihood to form two distinct possibilities: a layered or pillared structure\u003csup\u003e8\u0026ndash;11\u003c/sup\u003e. The layered frameworks could then be classified as a bilayer (ABA) or standard layered (AB) framework, yielding a more diverse field of hydrogen-bonded frameworks. The development and formation of hydrogen-bonded metal-organic frameworks (HBMOFs) will always be dependent on the building blocks used to construct the said HBMOFs. The common building blocks of our HBMOFs will contain a metal-organic carboxylic acid compound, which will yield the layer component, and the other component is an organic amine molecule, which is the director of the interlayer region. Hogan\u0026rsquo;s research group has shown a hydrogen-bonded framework created by Cu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e and DL-α-methylbenzylamine has included alcohol guest molecules within a bilayer formation. Using the same framework system, Hogan has also shown that this hydrogen-bonded framework could yield a layered structure when the guest molecules were changed to pyridine-based molecules.\u003c/p\u003e\u003cp\u003eGuest inclusion into metal-containing frameworks may possess some drawbacks or limitations. It has been widely shown that layered frameworks exhibit a close-packed nature,\u003csup\u003e7\u003c/sup\u003e yielding smaller channels or cavities that will afford guest inclusion. Pillared frameworks, on the other hand, will contain a more open channel\u003csup\u003e8\u003c/sup\u003e that would allow a greater efficiency for guest inclusion. All these layered solids are excellent candidates for host-guest chemistry (e.g. storage and separations), catalysis and photopolymerization reactions\u003csup\u003e12\u0026ndash;26\u003c/sup\u003e. Our focus in this study is to identify if the interlayer molecule (the amine molecule) directs the formation of the hydrogen-bonded framework (i.e. bilayer vs. layered) and if there a correlation between the size of the interlayer molecule and its ability to include guest molecules through a non-coordinative inclusion.\u003c/p\u003e"},{"header":"2. Materials and Methods","content":"\u003cp\u003eAll reagents and solvents used for the synthesis were commercially available and used without further purification. \u0026nbsp;Powder X-ray diffraction (PXRD) was collected using a Bruker D8 X-ray diffractometer with \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;Cu-K\u0026alpha; radiation (\u0026lambda; = 1.54060 \u0026Aring;) at 40 kV, 20 mA with a scanning rate of 5\u0026deg;/min and a step size of 0.015\u0026deg;. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e2.1. X-ray Crystallography\u003c/p\u003e\n\u003cp\u003eThe single crystal X-ray diffraction data were collected on a Bruker Photon 2 area detector diffractometer. The crystal was kept at 110 K during data collection. Using Olex2\u003csup\u003e27\u003c/sup\u003e, the structure was solved with the XT\u003csup\u003e28\u003c/sup\u003e structure solution program using Intrinsic Phasing and refined with the XL\u003csup\u003e29\u003c/sup\u003e refinement package using Least Squares minimisation. \u0026nbsp;Crystallographic details for \u003cstrong\u003e1 \u0026ndash; 5\u003c/strong\u003e are listed in Table 1, respectively. \u0026nbsp;Full crystallographic data can be found in the supplemental information. \u0026nbsp;CCDC numbers: 2386068, 2386070, 2386072, 2386074, and 2386075.\u003c/p\u003e\n\u003cp\u003e2.2. Synthesis of Crystalline Materials\u003c/p\u003e\n\u003cp\u003eThe crystalline materials were formed from slow evaporation after the reaction between Cu(HPDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e and phenethylamine, followed by the layering of the corresponding guest molecule. \u0026nbsp;In efforts to afford the empty framework, the synthesis was the same as above, but the layering molecule used was decane. \u0026nbsp;\u003c/p\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eIn this paper, we have created novel hydrogen-bonded frameworks that can include guest molecules. \u0026nbsp;We have developed four new host-guest hydrogen-bonded frameworks, listed as structures \u003cstrong\u003e2\u003c/strong\u003e \u0026ndash;\u003cstrong\u003e\u0026nbsp;5\u0026nbsp;\u003c/strong\u003eand the empty framework is labelled as \u003cstrong\u003e1\u003c/strong\u003e:\u003cstrong\u003e\u0026nbsp;(1) [phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e, (2) [phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;(1-pentanol), (3) [phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;(2-hexanol), (4) [phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;(benzyl alcohol), (5) [phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;(4-chlorobenzyl alcohol).\u003c/strong\u003e\u0026nbsp; The coordination of phenethylammnonium ions within the framework provides a structurally adaptable interlayer environment, facilitating the reversible accommodation of guest species. \u0026nbsp;The relative amount of flexibility has shown within recent hydrogen-bonded metal-organic frameworks developed by Beatty\u003csup\u003e7\u003c/sup\u003e and Hogan\u003csup\u003e10\u003c/sup\u003e\u003csub\u003e.\u0026nbsp;\u003c/sub\u003e The presented structures exhibit a layered formation (AB) where the Cu(HPDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e forms the lamellar portion of the layered section of the framework and the amine, phenethylamine, is used as the interlayer spacing between the layers. \u0026nbsp;An interesting feature of the framework is that the Cu (II) centre is bonded in an octahedral geometry with two water ligands in the axial position. \u0026nbsp;When compared back to Hogan\u0026rsquo;s previous Cu-based HBMOF there is a noticeable difference in the layer pattern formation. \u0026nbsp; The use of phenethylamine has afforded an octahedral metal centre, where previously used DL-\u0026alpha;-methylbenzylamine yielded a bilayer (ABA) framework. \u0026nbsp;The new complexes presented here were synthesized using Cu (HPDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e and phenethylamine and the unit cell of these components can be found in \u003cem\u003eFigure 1\u003c/em\u003e. \u0026nbsp;The crystalline frameworks are deemed isostructural with one another, where the lamellar metal-layer and the organic bilayer will remain the same in all structures. \u0026nbsp;The sole difference between the individual crystal structures will be dependent on the included guest molecule within the framework. The hydrogen-bonded framework forms through proton exchange between the Cu(HPDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e precursor and phenethylamine. \u0026nbsp;This acid-base interaction leads to the in-situ formation of phenethylammonium ions, which mediate the interlayer connectivity within the lamellar structure. \u0026nbsp;The acid-base reaction scheme mentioned previously will be a consistent reaction mechanism in all reported \u0026nbsp;crystal structures. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.\u003c/em\u003e\u003cstrong\u003e\u0026nbsp;[Phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e (1)\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eStructure \u003cstrong\u003e1\u003c/strong\u003e is a non-guest filled layered framework where the complete visualization of the hydrogen-bonded framework can be identified and viewed in \u003cem\u003eFigure 2\u003c/em\u003e. \u0026nbsp;In structure \u003cstrong\u003e1\u003c/strong\u003e, the metal-complex still contains an octahedral geometry, and the amine molecule is located in between the adjacent layers, serving as the interlayer spacer for the framework. \u0026nbsp;As previous mentioned, the layer region of the framework is formed through charge-assisted hydrogen bonding between the phenethylammonium ions and the copper-based pyridine dicarboxylate ion. \u0026nbsp; The phenethylammonium ions are directed in a face-to-face fashion, due to neighbouring \u0026pi;\u0026times;\u0026times;\u0026times;\u0026pi; interactions, between the layers. \u0026nbsp;This layer interaction yields the overall appearance of a closed-packed crystalline network, like Beatty and Hogan\u0026rsquo;s early work\u003csup\u003e2\u003c/sup\u003e, where the ability for guest insertion maybe difficult. \u0026nbsp;TGA analysis from the empty framework shows a small weight loss, around 4.92%, between 125\u0026deg;C and 175\u0026deg;C, where the calculated loss for two water molecules is 5.30% with in this HBMOF. \u0026nbsp;The small weight loss is in a similar agreement with the loss of two coordinated water molecules. Further reactions with linear chained alcohol and benzyl alcohol molecules will shows the framework\u0026rsquo;s ability to incorporate guest molecules. \u0026nbsp;A list of selected bond distances and bond angles are presented in Table 2.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 2\u0026nbsp;\u003c/strong\u003eSelected Bond Lengths and Bond Angles from Framework \u003cstrong\u003e1\u003c/strong\u003e\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eSelected Bond Lengths\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 114px;\"\u003e\n \u003cp\u003e( \u0026Aring; )\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eSelected Bond Angles\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e( ͦ )\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;Cu \u0026ndash; O1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 114px;\"\u003e\n \u003cp\u003e1.955 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eN2 \u0026ndash; Cu \u0026ndash; N1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e179.8 (3)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003e\u0026nbsp;Cu \u0026ndash; O5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 114px;\"\u003e\n \u003cp\u003e1.965 (6)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eO5 \u0026ndash; Cu \u0026ndash; O1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e179.6 (3)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eCu \u0026ndash; N1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 114px;\"\u003e\n \u003cp\u003e2.012 (7)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eO1 \u0026ndash; Cu \u0026ndash; N1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e96.2 (3)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eCu \u0026ndash; N2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 114px;\"\u003e\n \u003cp\u003e2.004 (7)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 186px;\"\u003e\n \u003cp\u003eO5 \u0026ndash; Cu \u0026ndash; N2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 138px;\"\u003e\n \u003cp\u003e83.4 (3)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cem\u003e3.2\u003cstrong\u003e\u0026nbsp;\u0026nbsp;\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e\u0026nbsp;[Phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026middot;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;1-pentanol (2)\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eStructure \u003cstrong\u003e2\u003c/strong\u003e is isostructural with structure \u003cstrong\u003e1\u003c/strong\u003e but contains an included 1-pentanol guest molecule. \u0026nbsp; The ratio of metal ion: guest within this structure is 1:1. The host framework to guest ratio can be seen in the expanded crystal structure as shown in \u003cem\u003eFigure 3\u003c/em\u003e. \u0026nbsp;The 1-pentanol guest molecules reside in between the layer spacers, the phenethylammonium ions, where the layer spacer exhibits the greatest disorder within this crystal structure. \u0026nbsp;The major disorder within this crystal structure lies with the orientation of the -NH\u003csub\u003e3\u003c/sub\u003e \u003csup\u003e+\u003c/sup\u003e, where the cationic region is displaced in two positions. \u0026nbsp;The extended layer formation shown is Figure 3 does not include the disordered nature of the phenethylammonium ion, simply illustrates the hydrogen-bonded directionality of the 2-D framework. \u0026nbsp;As seen from the TGA plots, there were two early temperature losses, below 100\u0026deg;C, which has often been associated with the loss of the guest molecule and the coordinated water ligands. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.3\u003c/em\u003e\u0026nbsp; \u0026nbsp;\u003cstrong\u003e\u0026nbsp;[Phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e \u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026middot;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;1-hexanol (3)\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eComplex\u003cstrong\u003e\u0026nbsp;3\u003c/strong\u003e is also isostructural with complex \u003cstrong\u003e1\u003c/strong\u003e but contains an included 1-hexanol guest molecule. \u0026nbsp;Complex \u003cstrong\u003e3\u003c/strong\u003e is similar in organization to complex \u003cstrong\u003e2\u003c/strong\u003e, with respect to the location of guest molecule and the hydrogen-bonding pattern. \u0026nbsp;The 1-hexanol guest molecule does not contain any disorder within its position in the crystal structure, it is noticed the 1-hexanol alternates the directionality of the hydroxyl group. \u0026nbsp;The major disorder in this crystal structure is found within the phenethylammonium interlayer spacers. \u0026nbsp;The ammonium head (NH\u003csub\u003e3\u0026nbsp;\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e) is found in a central location, whereas the ethyl chain has rotated into a different location to yield a two-fold disorder of the phenethyl group. \u0026nbsp;The hydrogen-bonded layer exhibits a slight larger spacing between neighboring Cu (PDCA) units, this is likely due to the disordered nature of the phenethylammonium cation. The crystal structure of the extended framework of complex \u003cstrong\u003e3\u003c/strong\u003e is found in \u003cem\u003eFigure 4a\u003c/em\u003e and thermogravimetric data showing guest loss can be found in \u003cem\u003eFigure 4b\u003c/em\u003e. \u0026nbsp;The TGA data shows a weight loss occurring from 50\u0026deg;C to around 90\u0026deg;C, which corresponds to the loss of the 1-hexanol guest molecule. \u0026nbsp; This initial weight loss of during this temperature range is roughly 10.3%. \u0026nbsp;The theoretical occupancy for this guest-included framework is 17.6%, keeping a consistent 1:1 ratio of host framework to guest molecule. \u0026nbsp;\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.4\u003c/em\u003e\u0026nbsp; \u0026nbsp;\u003cstrong\u003e\u0026nbsp;[Phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e \u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026middot;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;benzyl alcohol (4)\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eComplex\u003cstrong\u003e\u0026nbsp;4\u003c/strong\u003e is also isostructural with complex \u003cstrong\u003e1\u003c/strong\u003e but contains an included benzyl alcohol guest molecule. \u0026nbsp;Complex \u003cstrong\u003e4\u003c/strong\u003e is very similar to complex \u003cstrong\u003e2\u003c/strong\u003e, with respect to the location of guest molecule and the hydrogen-bonding pattern. \u0026nbsp;The benzyl alcohol guest molecule is disordered over two positions, giving the appearance of a diol species. \u0026nbsp;The benzyl alcohol molecule appears to be rotated and inverted within the channel to yield the two disordered sites. \u0026nbsp;In each case, the hydroxyl group is pointing outward to a neighbouring phenethyl ammonium group. \u0026nbsp; The crystal structure of the extended framework of complex 4 is found in \u003cem\u003eFigure 5a\u003c/em\u003e and thermogravimetric data showing guest loss can be found in \u003cem\u003eFigure 5b\u003c/em\u003e. \u0026nbsp;Thermal analysis indicates desorption within the 50 - 90\u0026deg;C range, corroborating guest incorporation that was observed crystallographically. \u0026nbsp;This initial weight loss of during this temperature range is roughly 11.7%. \u0026nbsp;The theoretical occupancy for this guest-included framework is 17.6%, keeping a consistent 1:1 ratio of host framework to guest molecule. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.5\u003c/em\u003e\u0026nbsp; \u0026nbsp;\u003cstrong\u003e\u0026nbsp;[Phenethylammonium]\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e \u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026middot;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;4-chlorobenzyl alcohol (5)\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eComplex\u003cstrong\u003e\u0026nbsp;5\u003c/strong\u003e is also isostructural with complex \u003cstrong\u003e1\u003c/strong\u003e but contains an included 4-chlorobenzyl alcohol guest molecule. \u0026nbsp;Complex 5 is very similar to complex 4, with respect to the location of guest molecule and the hydrogen-bonding pattern. \u0026nbsp;The 4-chlorobenzyl alcohol guest molecule is disordered over two positions, giving the appearance of a diol species. \u0026nbsp;In each case the hydroxyl group is pointing outward to a neighbouring phenethyl ammonium group. \u0026nbsp;The crystal structure of the extended framework of complex 5 is found in \u003cem\u003eFigure 6a\u003c/em\u003e and thermogravimetric data showing guest loss can be found in \u003cem\u003eFigure 6b\u003c/em\u003e. \u0026nbsp;The TGA data shows a weight loss occurring from 50\u0026deg;C to around 90\u0026deg;C, which corresponds to the loss of the 4-chlorobenzyl alcohol guest molecule. \u0026nbsp;This initial weight loss of during this temperature range is roughly 14.6%. \u0026nbsp;The theoretical occupancy for this guest-included framework is 18.3%, keeping a consistent 1:1 ratio of host framework to guest molecule. \u0026nbsp;\u0026nbsp;\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThis study presents the successful design and synthesis of a lamellar copper (II)-based hydrogen-bonded metal-organic framework (HBMOF) capable of incorporating a diverse range of alcohol guests, from linear alkyl chains to substituted benzyl alcohols. By utilizing phenethylamine as the interlayer spacer, the resulting framework adopts a standard AB-type lamellar framework with an octahedrally coordinated Cu (II) centre. The consistent structural motif across all five complexes underscores the robustness and modularity of the framework design.\u003c/p\u003e\u003cp\u003eThe inclusion of guest molecules within the interlayer regions was confirmed through single-crystal X-ray diffraction and thermogravimetric analysis (TGA), revealing notable guest-dependent variations in structural order and thermal behavior. These findings reinforce the tunable nature of hydrogen-bonded frameworks and highlight the significance of interlayer amine selection in dictating framework topology and inclusion properties. The demonstrated host\u0026ndash;guest versatility paves the way for future investigations into the selective sorption, separation, and functionalization capabilities of lamellar HBMOFs. Further studies will explore the role of guest polarity, molecular size, and substitution pattern on the dynamics and reversibility of inclusion processes within these adaptable frameworks.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003ch2\u003eConflicts of interest\u003c/h2\u003e\u003cp\u003eThere are no conflicts to declare.\u003c/p\u003e\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eCharles Gross, Thomas Johnson, and Jonah Bruyns contributed to the growth of the crystal and other experimental data. Christina Hogan gave analysis of data and assisted the primary PI with research development. Greg Hogan assisted in experimentations and writing of the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eThe authors would like to express their sincere appreciation to Dr. Joseph Reibenspies from the Department of Chemistry at Texas A\u0026amp;M University for assistance with the x-ray crystallography. The Welch foundation\u0026rsquo;s Departmental Grant for funding, Grant No. BZ-0052-20201025 and their Instrument Grant, Grant No. Q-BZ-0022-20240404.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eA. M. Beatty, \u003cem\u003eCoord, Chem. Rev\u003c/em\u003e. 246, (2003), 131.\u003c/li\u003e\n \u003cli\u003eS. A. Dalrymple, M. Parvez, G. K. Shimizu, \u003cem\u003eInorg. Chem\u003c/em\u003e.,41, (2002), 6986.\u003c/li\u003e\n \u003cli\u003eD. Braga, \u003cem\u003eDalton\u003c/em\u003e, (2000), 3705.\u003c/li\u003e\n \u003cli\u003eD. Braga, L. Maini, M. Polito, F. Grepioni, \u003cem\u003eStruct. Bonding (Berlin),\u003c/em\u003e 111, (2004), 1.\u003c/li\u003e\n \u003cli\u003eG. K. H. Shimzu, R. Vaidhyanathan, J. M. Taylor, \u003cem\u003eChem. Soc. Rev\u003c/em\u003e., 38, (2009), 1430.\u003c/li\u003e\n \u003cli\u003eA. Beatty and C. L. Chen, \u003cem\u003eJ. Am. Chem. Soc\u003c/em\u003e., 130, (2008), 17222.\u003c/li\u003e\n \u003cli\u003eA. Beatty, B. Helfrich, G. Hogan, and B. Reed, \u003cem\u003eCryst. Growth Des\u003c/em\u003e., 6, \u0026nbsp;(2006), 122.\u003c/li\u003e\n \u003cli\u003eG. Hogan, N. Rath and A. Beatty, Cryst. Growth Des., 11, (2011), 3740.\u003c/li\u003e\n \u003cli\u003eM. Fischer and A. Beatty, \u003cem\u003eCrystEngComm\u003c/em\u003e, 16, (2014), 7313.\u003c/li\u003e\n \u003cli\u003eG. J. Beach, C. E. Hogan, B. N. Besong, and G. A. Hogan\u003cem\u003e, J. Mol. Struc.., 1195,\u003c/em\u003e (2019), 5, 744.\u003c/li\u003e\n \u003cli\u003eH. H. Nguyen, C. E. Hogan, and G. A. Hogan, J. Chem. Crystallogr., 51, (2019), 82. \u0026nbsp;https://doi.org/10.1007/s10870-020-00838-1.\u003c/li\u003e\n \u003cli\u003eO. M. Yaghi, H. Li, C. Davis, D. Richardson and T. L. Groy, \u003cem\u003eAcc. Chem. Res., 31, (\u003c/em\u003e1998) 474.\u003c/li\u003e\n \u003cli\u003eA. Pivovar, K. Holman and M. Ward, \u003cem\u003eChem. Mater.,\u003c/em\u003e 13, (2001), 3018.\u003c/li\u003e\n \u003cli\u003eK. Endo, T. Koike, T. Sawaki, O. 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Cryst., 42, (2009) \u0026nbsp;339.\u003c/li\u003e\n \u003cli\u003eG. M. Sheldrick (2015). Acta Cryst. A71, 3-8.\u003c/li\u003e\n \u003cli\u003eG. M. Sheldrick (2008). Acta Cryst. A64, 112-122.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table","content":"\u003cp\u003eTable 1 is 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":"journal-of-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7255550/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7255550/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe continuous investigation of a copper (II) component that used in developing novel hydrogen-bonded metal-organic frameworks (HBMOFs).\u0026nbsp; In this investigation, the copper (II) compound is reacted with phenethylamine, resulting in a complex containing a lamellar framework, which exist as a 6-coordinate copper (II) center.\u0026nbsp; The use of the phenethylamine compound will afford an extended interlayer, when compared to previous (HBMOFs).\u0026nbsp; This layered framework has the ability to include a variety of guest molecules, ranging from alkyl alcohols to benzyl alcohols.\u0026nbsp; The discussion of four guest included hydrogen-bonded frameworks will be discussed herein and will be compared with an empty framework: (1) [phenethylammonium]\u003csub\u003e2\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e, (2) [phenethyllammonium]\u003csub\u003e2\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e·(1-pentanol), (3) [phenethylammonium]\u003csub\u003e2\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e·(1-hexanol), (4) [phenethylammonium]\u003csub\u003e2\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e·(benzyl alcohol), (5) [phenethylammonium]\u003csub\u003e2\u003c/sub\u003eCu(PDCA)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e·(4-chlorobenzyl alcohol).\u003c/p\u003e","manuscriptTitle":"Alcohol Guest Molecule Capture in a Novel Copper (II) Hydrogen-Bonded Metal- Organic Framework (HBMOF)","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-08-20 13:08:42","doi":"10.21203/rs.3.rs-7255550/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-09-08T14:12:22+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-02T23:50:52+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"288376566200723288080361305635943794475","date":"2025-08-27T16:31:21+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-08-25T17:10:36+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"185758021017857781480110334292385433692","date":"2025-08-18T16:10:53+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-08-12T12:52:54+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-08-08T06:40:07+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-08-08T06:38:33+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Chemical Crystallography","date":"2025-07-30T17:55:42+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b0efb5aa-ea62-4ebf-828d-691cee228061","owner":[],"postedDate":"August 20th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-01-19T17:22:00+00:00","versionOfRecord":{"articleIdentity":"rs-7255550","link":"https://doi.org/10.1007/s10870-025-01080-3","journal":{"identity":"journal-of-chemical-crystallography","isVorOnly":false,"title":"Journal of Chemical Crystallography"},"publishedOn":"2026-01-14 16:28:38","publishedOnDateReadable":"January 14th, 2026"},"versionCreatedAt":"2025-08-20 13:08:42","video":"","vorDoi":"10.1007/s10870-025-01080-3","vorDoiUrl":"https://doi.org/10.1007/s10870-025-01080-3","workflowStages":[]},"version":"v1","identity":"rs-7255550","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7255550","identity":"rs-7255550","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}