Pyridinedicarboxylic Acids as Versatile Building Blocks for Coordination-Driven Self-Assembly: Solvent-Induced Macrocycle and Coordination Polymer Formation upon Combination of 2,5-Pyridinedicarboxylate with Diorganotin Moieties

Abstract

Ligands derived from 2,x- and 3,y-pyridinedicarboxylic acid (x = 3–6; y = 4–5) are widely used building blocks for the formation of metal-coordination polymers (MCPs), as they show a large variety of bridging modes and angles. Metal complexation occurs either only with the carboxylate groups or through N,O-chelate ring formation. In this contribution, the supramolecular chemistry and solvatomorphism of diorganotin complexes with 2,5-pyridinedicarboxylate (25pdc) formed in the presence of a series of coordinating and noncoordinating solvents were explored in detail. Five novel diorganotin 25pdc’s of composition [Me2Sn­(25pdc)­(py)]3­·3.04C5H5N­·1.86H2O (1), {[Me2Sn­(25pdc)]­·[Me2Sn­(25pdc)­(H2O)]} n ­2nC7H8O (2), {[nBu2Sn­(25pdc)]4} n ­·4nC6H5NO2 (3), [nBu2Sn­(25pdc)­(gly)] n (4), and {[nBu2Sn­·(25pdc)]3} n ­·nCHCl3 (5) were achieved and analyzed in the context of previously reported tri- and diorganotin complexes with the same ligand. The comparative study revealed that upon coordination to diorganotin species the ligand exhibits N,O-chelate ring formation with the carboxylate group in the 2-position and bridging to other tin atoms primarily by the 5-carboxylate group, giving macrocyclic, one-, two-, or three-dimensional MCPs. On the contrary, triorganotin moieties are mostly bound only by the ligand carboxylate groups without N→Sn binding. The assemblies of diorganotin 25pdc’s mostly contain trinuclear or tetranuclear macrocycles with a large predominance of the generally uncommon [3 + 3] metal–organic aggregates. For the trinuclear macrocycles, different configurations having 12-, 18-, 21-, or 27-membered rings were encountered. The metal atoms in diorganotin 25pdc’s prefer pentagonal-bipyramidal environments, which are achieved through coordination by solvent molecules (H2O, DMSO, py) or intermolecular O→Sn bond formation. In solution, di-n-butyltin 25pdc exhibits supramolecular isomerism, giving a tetrameric aggregate in the noncoordinating solvent chloroform and a trimeric species in the presence of coordinating solvents, such as DMSO, pyridine, or methanol, due to solvent→Sn bond formation.

Design of Promising Heptacoordinated Organotin (IV) Complexes-PEDOT: PSS-Based Composite for New-Generation Optoelectronic Devices Applications

“…Their structural diversity has been related to the coordination modes and angles of the COO moiety [37,38]. Additionally, carboxylates are excellent building blocks in the formation of metal-coordination polymers, macrocycles and cages [39,40]. Organotin also possess a wide range of medicinal and industrial applications, as potential agents in cancer chemotherapy, catalysis of urethane, PVC stabilization, silicone curing and antifouling [41][42][43][44].…”

Diol Struts Stabilize the Structure of a 3D Hydrogen-Bonded Framework with Large Cavities: Inclusion of Solvated Nile Red in the Solid State

“…In the presence of 1,2-ethanediol (gly), the reaction of nBu 2 SnO with 25pdcH 2 resulted in the 1D coordination polymer [nBu 2 Sn(25pdc)-(gly)] n , as shown by SCXRD analysis. 9 For the products formed in the presence of 1,3-propane-and 1,6-hexanediol, crystals suitable for SCXRD could not be achieved and structural data are not available so far.…”

“…1 Aside from the importance for biological processes, molecular assemblies are substantial for molecular recognition, crystal engineering, materials science, and catalysis, among others. 2−7 In addition, using metal−ligand bonds, coordination-driven self-assembly of metal−organic aggregates and networks has proven to be an efficient and powerful approach for constructing supramolecular coordination compounds with controllable shapes and sizes, including macrocycles, 8,9 cages, 10,11 capsules, 12,13 and metal−organic frameworks (MOFs) 14,15 or metal coordination polymers (MCPs). 16−18 Related research studies in the recent past have contributed to the development of an extensive and interesting panorama of applications.…”

“…Reactions of diorganotin (R 2 Sn) moieties with the heteroditopic ligand 2,5-pyridinedicarboxylate (25pdc) are prone to supramolecular isomerism, as shown by previous reports from our research group. 9,57 This is because tin-carboxylate ligand combinations proceed with variations in the metal coordination polyhedron and because of the property of organic carboxylates to engage in different chelation modes (monodentate, bidentate, and bridging). The product composition and tin coordination geometry depend mostly on the organic substituents attached to the metal atom and the solvent employed in the reaction.…”

Dinuclear Organotin Building Blocks and their Conversion into a Tetranuclear Macrocycle Containing Sn−O−Sn Linkages

“…[19][20][21][22][23] Changes of the substitution pattern at the tin atoms modify the Lewis acidity and steric hindrance, which can be an important requisite for the successful formation of macrocyclic or cage-type structures. [11,[24][25][26][27] Being Lewis acids, four-coordinate tin compounds count on the possibility of coordination number increase, enabling linkages with other compounds, e. g. solvent or guest molecules. [28] Because of these attributes, organotin compounds with interesting properties concerning the catalysis of transesterification and CÀ C coupling reactions, [29][30] anion and molecular recognition, [31][32][33][34][35] materials chemistry, [36][37][38] or biological activity [39][40][41][42] have been developed.…”