Syntheses, Structures And Properties Of Coordination Polymers Based On3,5-bis-carboxymethoxy-benzoic Acid

Coordination polymers based on the variety of coordination modes of aromatic multi-carboxylic ligands through self-assembly have been received more and more interest due to their potential applications in many fields. We have successfully designed a tricarboxylate ligand,3,5-bis-carboxymethoxy-benzoic acid (H3L), which possesses one rigid carboxyl group and two flexible carboxyl groups, and have synthesized thirteen unique complexes under solvothermal and hydrothermal reactions:Namely [Zn2(L)(bpp)(OH)]·0.5H2O (1),[Cd3(L)2(bpp)2(H2O)6]·2H2O (2),[Cd3(L)2(2,2’-bipy)3(H2O)4]·5.5H2O (3),[CdNa(L)(H2O)]·0.5H2O (4),[Cd2(L)(bimb)Cl(H2O)2]·H2O (5),[Cd2(L)(phen)(OH)]·4H2O (6),[Mn3(L)2(phen)2](7),[Mn3(L)2(4,4’-bipy)(H2O)2]·2H2O (8),[MnⅡ3MnⅢ(L)2(OH)3(H2O)]·2.5H2O (9),[MnⅡ3MnⅢ4(L)4(OH)6(H2O)2]·4H2O (10),[MnⅡ3MnⅢ4(L)4(OH)4(Cl)2(H2O)2]·6H2O (11),[Co3(L)2(4,4’-bipy)2(H2O)8](12) and [Cu3(L)2(bimb)3]·4H2O (13). They display different topological structures.1is an uninodal4-connected2D square grid network based on binuclear zinc clusters.2is2D wavelike layer structure and further linked by hydrogen bonds into the final3D (5,6,6)-connected topology network.3is3-connected2D topology network and the2,2’-bipy ligands decorate in two different types. It is further consolidated by intermolecular and intramolecular O-H…O hydrogen bonds.4is a (4,8)-connected2D topology network with heterocaryotic {Cd2Na2} clusters and L3-ligands.5can be rationalized as a (3,10)-connected3D topology network with tetranuclear {Cd4Cl2} clusters and L3-ligands.6is a (3,6)-connected3D topology network based on tetranuclear cadmium clusters.7and8are both MnⅡ complexes, which present3D binodal (3,6)-connected rutile network and (3,8)-connected tfz-d network based on trinuclear manganese clusters, respectively.9-11are mixed-valent MnⅡ/MnⅢ complexes.9can be rationalized as a new binodal (5,12)-connected3D topology network based on tetranuclear manganese clusters.10and11are isostructural and present binodal (3,12)-connected2D topology network based on heptanuclear manganese clusters.12presents2D grid structure and further linked by hydrogen bonds into the final superamolecular network.13shows a trinodal (3,4,4)-connected3D topology network.These complexes were determined by single-crystal X-ray diffraction analyses, elemental analyses, IR and thermal analyses. Photoluminescence studies revealed that complexes1-6display strong fluorescent emission bands in the solid state at room temperature.