H-Bonded and metal(ii)-organic architectures assembled from an unexplored aromatic tricarboxylic acid: structural variety and functional properties

This study reports the application of an aromatic tricarboxylic acid, 2,5-di(4-carboxylphenyl)nicotinic acid (H3dcna) as a versatile and unexplored organic building block for assembling a new series of metal(ii) (M = Co, Ni, Zn, Fe, and Mn) complexes and coordination polymers, namely [M(Hdcna)(phen)2(H2O)]·H2O (M = Co (1), Ni (2)), [Zn(µ-Hdcna)(phen)]n(3), [Co(µ-Hdcna)(bipy)(H2O)2]n·nH2O (4), [Zn2(µ-Hdcna)2(bipy)2(H2O)4]·6H2O (5), [Zn(µ3-Hdcna)(H2biim)]n(6), [Ni2(Hdcna)2(µ-bpb)(bpb)2(H2O)4] (7), [Fe(µ4-Hdcna)(µ-H2O)]n·nH2O (8), and [Mn3(µ5-dcna)2(bipy)2(H2O)2]n·2nH2O (9). Such a diversity of products was hydrothermally prepared from the corresponding metal(ii) salts, H3dcna as a principal multifunctional ligand, and N-donor mediators of crystallization (1,10-phenanthroline, phen; 2,2'-bipyridine, bipy; 2,2'-biimidazole, H2biim; or 1,4-bis(pyrid-4-yl)benzene, bpb). The obtained products1-9were fully characterized by standard methods (elemental analysis, FTIR, TGA, PXRD) and the structures were established by single-crystal X-ray diffraction. These vary from the discrete monomers (1,2) and dimers (5,7) to the 1D (3,4,6) and 2D (8,9) coordination polymers (CPs). Structural and topological characteristics of hydrogen-bonded or metal-organic architectures in1-9were highlighted, revealing that their structural multiplicity depends on the type of metal(ii) source and crystallization mediator. Thermal stability as well as luminescent, magnetic, or catalytic properties were explored for selected compounds. In particular, the zinc(ii) derivatives3,5, and6were applied as efficient heterogeneous catalysts for the cyanosilylation of aldehydes with trimethylsilyl cyanide at room temperature. The catalytic reactions were optimized by tuning the different reaction parameters (solvent composition, time, catalyst loading) and the substrate scope was also explored. Compound5revealed superior catalytic activity leading to up to 75% product yields, while maintaining its original performance upon recycling for at least four reaction cycles. Finally, the obtained herein products represent the unique examples of coordination compounds derived from H3dcna, thus opening up the use of this multifunctional tricarboxylic acid for generating complexes and coordination polymers with interesting structures and functional properties. © The Royal Society of Chemistry 2020.

Gu J.-Z.1 , Wan S.-M.1 , Kirillova M.V.2 , Kirillov A.M. 2, 3
Royal Society of Chemistry
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  • 1 State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China
  • 2 Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
  • 3 Research Institute of Chemistry, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., Moscow, 117198, Russian Federation
Aromatic polymers; Catalysis; Catalyst activity; Coordination reactions; Dimers; Hydrogen bonds; Manganese compounds; Metals; Organometallics; Single crystals; Coordination compounds; Coordination Polymers; Functional properties; Heterogeneous catalyst; Metal-organic architecture; Single crystal x-ray diffraction; Topological characteristics; Trimethylsilyl cyanide; Zinc compounds
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