{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,26]],"date-time":"2025-10-26T21:38:34Z","timestamp":1761514714589,"version":"build-2065373602"},"reference-count":44,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2021,2,3]],"date-time":"2021-02-03T00:00:00Z","timestamp":1612310400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100010843","name":"Guangzhou Science, Technology and Innovation Commission","doi-asserted-by":"publisher","award":["201904010381"],"award-info":[{"award-number":["201904010381"]}],"id":[{"id":"10.13039\/501100010843","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["CEECIND\/03708\/2017, LISBOA-01-0145-FEDER-029697, PTDC\/QUI-QIN\/3898\/2020, and UID\/QUI\/00100\/2013"],"award-info":[{"award-number":["CEECIND\/03708\/2017, LISBOA-01-0145-FEDER-029697, PTDC\/QUI-QIN\/3898\/2020, and UID\/QUI\/00100\/2013"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100018647","name":"RUDN University","doi-asserted-by":"publisher","award":["RUDN University Program 5-100"],"award-info":[{"award-number":["RUDN University Program 5-100"]}],"id":[{"id":"10.13039\/501100018647","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>Three 2D coordination polymers, [Cu2(\u00b54-dpa)(bipy)2(H2O)]n\u22196nH2O (1), [Mn2(\u00b56-dpa)(bipy)2]n (2), and [Zn2(\u00b54-dpa)(bipy)2(H2O)2]n\u00b72nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2\u2032,4\u2032-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2\u2032-bipyridine (bipy) as a crystallization mediator. Compounds 1\u20133 were obtained as crystalline solids and fully characterized. The structures of 1\u20133 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1\u20133 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.<\/jats:p>","DOI":"10.3390\/catal11020204","type":"journal-article","created":{"date-parts":[[2021,2,3]],"date-time":"2021-02-03T11:54:31Z","timestamp":1612353271000},"page":"204","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes"],"prefix":"10.3390","volume":"11","author":[{"given":"Yu","family":"Li","sequence":"first","affiliation":[{"name":"Guangdong Research Center for Special Building Materials and Its Green Preparation Technology\/Foshan Research Center for Special Functional Building Materials and Its Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China"}]},{"given":"Chumin","family":"Liang","sequence":"additional","affiliation":[{"name":"Guangdong Research Center for Special Building Materials and Its Green Preparation Technology\/Foshan Research Center for Special Functional Building Materials and Its Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China"}]},{"given":"Xunzhong","family":"Zou","sequence":"additional","affiliation":[{"name":"Guangdong Research Center for Special Building Materials and Its Green Preparation Technology\/Foshan Research Center for Special Functional Building Materials and Its Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China"}]},{"given":"Jinzhong","family":"Gu","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China"}]},{"given":"Marina V.","family":"Kirillova","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural and Departamento de Engenharia Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2052-5280","authenticated-orcid":false,"given":"Alexander M.","family":"Kirillov","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural and Departamento de Engenharia Qu\u00edmica, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"},{"name":"Research Institute of Chemistry, Peoples\u2019 Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., 117198 Moscow, Russia"}]}],"member":"1968","published-online":{"date-parts":[[2021,2,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Kaskel, S. (2016). The Chemistry of Metal-Organic Frameworks, 2 Volume Set: Synthesis, Characterization, and Applications, John Wiley & Sons.","DOI":"10.1002\/9783527693078"},{"key":"ref_2","unstructured":"Batten, S.R., Neville, S.M., and Turner, D.R. (2009). Coordination Polymers: Design, Analysis and Application, RSC."},{"key":"ref_3","unstructured":"MacGillivray, L.R., and Lukehart, C.M. (2014). Metal-Organic Framework Materials, John Wiley & Sons."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2781","DOI":"10.1039\/b305705b","article-title":"Engineering coordination polymers towards applications","volume":"2003","author":"Janiak","year":"2003","journal-title":"Dalton Trans."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2334","DOI":"10.1002\/anie.200300610","article-title":"Functional Porous Coordination Polymers","volume":"43","author":"Kitagawa","year":"2004","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_6","doi-asserted-by":"crossref","unstructured":"Tibbetts, I., and Kostakis, G.E. (2020). Recent Bio-Advances in Metal-Organic Frameworks. Molecules, 25.","DOI":"10.3390\/molecules25061291"},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"G\u00f3mez-Avil\u00e9s, A., Muelas-Ramos, V., Bedia, J., Rodriguez, J.J., and Belver, C. (2020). Thermal post-treatments to enhance the water sta-bility of NH2-MIL-125(Ti). Catalysts, 10.","DOI":"10.3390\/catal10060603"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"6925","DOI":"10.1021\/jacs.0c01769","article-title":"Splitting mono- and di-branched alkane isomers by a robust aluminum-based metal-organic framework material with optimal pore dimensions","volume":"142","author":"Yu","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1968","DOI":"10.1021\/acs.accounts.8b00658","article-title":"Microporous Metal\u2013Organic Frameworks for Adsorptive Separation of C5\u2013C6 Alkane Isomers","volume":"52","author":"Wang","year":"2019","journal-title":"Acc. Chem. Res."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1126","DOI":"10.1021\/cr200101d","article-title":"Luminescent Functional Metal\u2013Organic Frameworks","volume":"112","author":"Cui","year":"2011","journal-title":"Chem. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Bedia, J., Muelas-Ramos, V., Pe\u00f1as-Garz\u00f3n, M., G\u00f3mez-Avil\u00e9s, A., Rodriguez, J.J., and Belver, C. (2019). A Review on the Synthesis and Characterization of Metal Organic Frameworks for Photocatalytic Water Purification. Catalysts, 9.","DOI":"10.3390\/catal9010052"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"11096","DOI":"10.1021\/ic101668f","article-title":"Self-assembled 3D heterometallic CuII\/FeII coordination polymers with octahedral net skeletons: Structural features, molecular magnetism, thermal and oxidation catalytic properties","volume":"49","author":"Karabach","year":"2010","journal-title":"Inorg. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"356","DOI":"10.1021\/acs.accounts.8b00521","article-title":"Metal\u2013Organic Frameworks for Photocatalysis and Photothermal Catalysis","volume":"52","author":"Xiao","year":"2019","journal-title":"Acc. Chem. Res."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2403","DOI":"10.1021\/acs.inorgchem.8b02926","article-title":"Metal\u2212organic architectures assembled from multifunctionalpolycarboxylates: Hydrothermal self-assembly, structures, andcatalytic activity in alkane oxidation","volume":"58","author":"Gu","year":"2019","journal-title":"Inorg. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5875","DOI":"10.1021\/acs.inorgchem.9b00242","article-title":"Cobalt(II) Coordination Polymers Assem-bled from UnexploredPyridine-Carboxylic Acids: Structural Diversity and CatalyticOxidation of Alcohols","volume":"58","author":"Gu","year":"2019","journal-title":"Inorg. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"14723","DOI":"10.1039\/D0DT03025B","article-title":"Metal-organic frameworks as acid- and\/or base-functionalized catalysts for tandem reac-tions","volume":"49","author":"Zhang","year":"2020","journal-title":"Dalton Trans."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2010","DOI":"10.1021\/acs.cgd.8b01462","article-title":"Flexible Zn-MOF Exhibiting Selective CO2 Adsorption and Efficient Lewis Acidic Catalytic Activity","volume":"19","author":"Agarwal","year":"2019","journal-title":"Cryst. Growth Des."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"4044","DOI":"10.1039\/D0DT00157K","article-title":"Metal-dependent photosensitivity of three isostructural 1D CPs based on the 1,1\u2032-bis(3-carboxylatobenzyl)-4,4\u2032-bipyridinium moiety","volume":"49","author":"Liu","year":"2020","journal-title":"Dalton Trans."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"4658","DOI":"10.1021\/acs.cgd.6b00735","article-title":"Srtructurally distinct metal\u2212organic and H-bonded networks derivedfrom 5-(6-carboxypyridin-3-yl)isophthalic acid: Coordination and template effect of 4,4\u2032-bipyridine","volume":"16","author":"Gu","year":"2016","journal-title":"Cryst. Grwoth Des."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"753","DOI":"10.1039\/C3CE42007H","article-title":"Solvent-induced structural diversities from discrete cup-shaped Co8 clusters to Co8 cluster-based chains accompanied by in situ ligand conversion","volume":"16","author":"Han","year":"2014","journal-title":"Cryst. Eng. Comm."},{"key":"ref_21","first-page":"1705","article-title":"Syntheses of two nickel(II) coordination compounds based on a rigid linear tricarboxylic acid","volume":"35","author":"Zou","year":"2019","journal-title":"Chin. J. Inorg. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3312","DOI":"10.1021\/cg300442b","article-title":"pH and Auxiliary Ligand Influence on the Structural Variations of 5(2\u2032-Carboxylphenyl) Nicotate Coordination Polymers","volume":"12","author":"Gu","year":"2012","journal-title":"Cryst. Growth Des."},{"key":"ref_23","first-page":"727","article-title":"Temperature-dependent syntheses of two manganese(II) coordination com-pounds based on an ether-bridged tetracarboxylic acid","volume":"39","author":"Li","year":"2020","journal-title":"Chin. J. Struct. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1237","DOI":"10.1021\/acs.cgd.9b01499","article-title":"Side chain induced self-assembly and selective catalytic oxidation activity of copper(I)-coper(II)-N4 complexes","volume":"20","author":"Hou","year":"2020","journal-title":"Cryst. Growth Des."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"7197","DOI":"10.1039\/D0DT01261K","article-title":"H-bonded and metal(II)-organic architectures assembled from an unex-plored aromatic tricarboxylic acid: Structural variety and functional properties","volume":"49","author":"Gu","year":"2020","journal-title":"Dalton Trans."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3649","DOI":"10.1021\/cr9902906","article-title":"Cyanohydrins in Nature and the Laboratory: Biology, Preparations, and Synthetic Applications","volume":"99","author":"Gregory","year":"1999","journal-title":"Chem. Rev."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2752","DOI":"10.1002\/anie.200300604","article-title":"Chemically catalyzed asymmetric cyanohydrin syntheses","volume":"43","author":"Brunel","year":"2004","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"12276","DOI":"10.1002\/chem.201101195","article-title":"Mild and Efficient Trimethylsilylcyanation of Ketones Catalysed by PNP Chloride","volume":"17","author":"Lacour","year":"2011","journal-title":"Chem. Eur. J."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1021\/cr60132a001","article-title":"The preparation of nitriles","volume":"42","author":"Mowry","year":"1948","journal-title":"Chem. Rev."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"5557","DOI":"10.1002\/ejic.201600902","article-title":"Zinc(II) and Copper(II) Metal-Organic Frameworks Constructed from a Terphenyl-4,4\u2032\u2032-dicarboxylic Acid Derivative: Synthesis, Structure, and Catalytic Application in the Cyanosilylation of Aldehydes","volume":"2016","author":"Karmakar","year":"2016","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1455","DOI":"10.1007\/s10876-019-01589-6","article-title":"Three-dimensional Ni(II)-MOF containing anasymmetric pyridyl-carboxylate ligand: Catalytic cyanosilylation of aldehydes and inhibits human promyelocytic leukemia cancer cells","volume":"30","author":"Xi","year":"2019","journal-title":"J. Clust. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2570","DOI":"10.1039\/C7CE00219J","article-title":"Introducing 2-(2-carboxyphenoxy)terephthalic acid as a new versatile building block for design of diverse coordination polymers: Synthesis, structural features, luminescence sensing, and magnetism","volume":"19","author":"Gu","year":"2017","journal-title":"CrystEngComm"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1069","DOI":"10.1021\/cg201459k","article-title":"Topologically Unique 2D Heterometallic CuII\/Mg Coordination Polymer: Synthesis, Structural Features, and Catalytic Use in Alkane Hydrocarboxylation","volume":"12","author":"Kirillov","year":"2012","journal-title":"Cryst. Growth Des."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"16082","DOI":"10.1039\/D0NJ03628E","article-title":"Introducing a flexible tetracarboxylic acid linker into functional coordination polymers: Synthesis, structural traits, and photocatalytic dye degradation","volume":"44","author":"Chen","year":"2020","journal-title":"New J. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"761","DOI":"10.1016\/j.molstruc.2017.08.064","article-title":"Auxiliary ligands induced two new Zn(II) compounds with the structural variations from 2D layer to 3D framework: Syntheses, structures and photoluminescent properties","volume":"1149","author":"Yu","year":"2017","journal-title":"J. Mol. Struct."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"4557","DOI":"10.1039\/C9CE00542K","article-title":"Three coordination polymers based on 3-(3\u2032,5\u2032-dicarboxylphenoxy)phthalic acid and auxiliary N-donor ligands: Syntheses, structures, and highly selective sensing for nitro explosives and Fe3+ ions","volume":"21","author":"Wang","year":"2019","journal-title":"CrystEngComm"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"10908","DOI":"10.1039\/C7DT01742A","article-title":"Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block","volume":"46","author":"Gu","year":"2017","journal-title":"Dalton Trans."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"5886","DOI":"10.1021\/acs.inorgchem.6b00186","article-title":"Silver(I) 1,3,5-Triaza-7-phosphaadamantane Coordination Polymers Driven by Substituted Glutarate and Malonate Building Blocks: Self-Assembly Synthesis, Structural Features, and Antimicrobial Properties","volume":"55","author":"Jaros","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"12711","DOI":"10.1039\/C5DT01456E","article-title":"Solvent-free heterogeneous catalysis for cyanosilylation in a dynamic cobalt-MOF","volume":"44","author":"Cui","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_40","first-page":"3","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Cryst."},{"key":"ref_41","first-page":"194","article-title":"Platon Program","volume":"46","author":"Spek","year":"1990","journal-title":"Acta Cryst."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"3576","DOI":"10.1021\/cg500498k","article-title":"Applied Topological Analysis of Crystal Structures with the Program Package ToposPro","volume":"14","author":"Blatov","year":"2014","journal-title":"Cryst. Growth Des."},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Llabr\u00e9s i Xamena, F.X., and Gascon, J. (2013). Metal-Organic Frameworks as Heterogeneous Catalysts, Royal Society of Chemistry.","DOI":"10.1039\/9781849737586"},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Garc\u00eda, H., and Naval\u00f3n, S. (2018). Metal-Organic Frameworks: Applications in Separations and Catalysis, John Wiley & Sons.","DOI":"10.1002\/9783527809097"}],"container-title":["Catalysts"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4344\/11\/2\/204\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T05:19:36Z","timestamp":1760159976000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4344\/11\/2\/204"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,2,3]]},"references-count":44,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2021,2]]}},"alternative-id":["catal11020204"],"URL":"https:\/\/doi.org\/10.3390\/catal11020204","relation":{},"ISSN":["2073-4344"],"issn-type":[{"type":"electronic","value":"2073-4344"}],"subject":[],"published":{"date-parts":[[2021,2,3]]}}}