Syntheses, Structures, and Properties of a Series of Multidimensional Metal-Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N-Donor Ancillary Ligands

Hydrothermal reactions of aromatic 3,3',5,5'-biphenyl-tetracarboxylic acid (H(4)bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M(H(2)bpt)(Hpptp)](n) (M = Mn (1), Fe (2), Co (3), and Zn (4)), [Mn-2(bPt)(Hpptp)(2)](n) (5), {[Zn-3(Hbpt)-(bpt)(H2O)(2)][(4,4'-H(2)bmib)(0.5)]center dot H2O}(n) (6), {[Cu(bpt)(0.5)(4,4'-bimbp)]center dot H2O}(n) (7), {[Co(H(2)bpt) (2,7-dfo)center dot H2O}(n) (8), and {[Ni-2(bpt) (4,4'-bibp)(2.5)(H2O)]center dot 3(H2O)}(n) (9) (Hpptp = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine; 4,4'-bmib = 4,4'-bis(2-methylimidazol-1-yl)benzene; 4,4'-bimbp = 4,4'-bis(imidazol-1-ylmethyl)biphenyl; 2,7-dfo = 2,7-di(imidazo-1-ly)-9H-fluoren-9-one; 4,4'-bibp = 4,4'-bis(imidazol)-biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1-4 are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer pi center dot center dot center dot pi interactions into a 3D supramolecular structure. Complex 5 displays a pillared-layer 3D porous network with a (6(2).8)(2)(6(2).8(2).10(2)) topology. Compound 6 shows an unprecedented 3D host-framework consisting of Zn-6 clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schlafli symbol of (4(10).6(5)) (4(19).6(16).8) (4(6).6(4)) (4(7).6(3))(2). The topology of 7 is an unprecedented binodal (4,4)-connected 3D network with the Schlafli symbol of (6(2).8(4))(4(2).8(2))(2). Complex 8 exhibits a 3D (6(6)) structure with left- and right-handed helical chains arranged alternately. Complex 9 is a novel trinodal (4,4,5)-connected 3D framework with the Schlafli symbol of (6(4).8(2))(6(5).8)(6(8).8(2)). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for 6, binodal (4,4)-connected for 7, and trinodal (4,4,5)-connected for 9 have never been documented to date. Moreover, the luminescent properties of 4 and 6 have been investigated.