Seven structural versatile coordination polymers based on a flexible bis(triazole) and polycarboxylate coligands: syntheses, structures and properties

Seven coordination polymers {[Mn(tmtz)(0.5)(OH-bdc)(H2O) 2]? 2.75H(2)O} n (1), [Mn(tmtz) 1.5(1,3-bdc)](n)< 2 >, [Mn(tmtz)(1,4-bdc)](n) (3), [Co(tmtz)(oba](n) (4), {[Co-4(tmtz) 2(bptc)(2)(H2O) 7].3.5H(2)O} n (5), {[Ni(tmtz) 1.5(1,3bdc)]? 0.5H(2)O}(n) (6), [Ni(tmtz)(oba)(H2O)](n) (7) < tmtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, OH-bdc = 5-hydroxy-1,3-benzenedicarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate, 1,4-bdc = 1,4-benzenedicarboxylate, H(2)oba = 4,49-oxybis(benzoic acid), bptc = 3,39,4,49-benzophenonetetracarboxylate) have been synthesized and structurally characterized. 1 exhibits a 1D ladder structure and a 3D supramolecular architecture. 2 and 6 have similar 5-connected 2D networks through the 1,3-bdc ligand connecting [M(tmtz) 1.5] n 1D ladders, with the point symbol (48 ? 62). 3 has a (4,6)-connected 3D fsc network with a point symbol of (4(4) . 6(2))(4(4). 6(10).8). 4 shows a 1D tubular-like chain. 5 exhibits a complicated (3,4,4)-connected 3D network with a point symbol of (4.10.12)(2)(4?.8(3).10(2)12(2))(2)(8(2) .10(2).12(2)). Such a (3,4,4)connected 3D network is unprecedented to the best of our knowledge. 7 displays a 2D (4,4) network which crystallizes in the chiral orthorhombic space group P2(1)2(1)2(1). The results indicate that the central metal ions, polycarboxylate and flexible triazole co-ligands have a great effect on the formation and the structures of the coordination polymers. The thermal stability and luminescence were investigated. The crystal structures and solid-state circular dichroism (CD) spectra measurements confirmed the occurrence of the spontaneous resolution of 7 and demonstrated that the resulting crystal of 7 is a racemic mixture.