Syntheses Of A Series Of Coordination Polymers Based On Aromatic N-donor Ligands:Catalytic Conversion And Fluorescence Sensing Towards To Nitro-aromatic Compounds

Coordination polymers possess features of inorganic-organic hybrid functional materials; is becoming a hot research focus in advanced functional materials gradually. In this paper, the flexible N-containing ligand TPOM, rigid classic tripodal ligand tib and a series of V-shaped ligands (1,3-dpb, BIDPE, BPDPE, PIDPE) were selected as main ligands, and various carboxylic acid as auxiliary ligands to synthesize twelve brand new coordination polymers, namely,{[Cu2(TPOM)(ddpa)2]}n (1)、 {[Cu(tib)2(H2O)2](NO3)2}n (2)、{[Cd(1,3-bdc)(dpb)]-2H2O}n (3), [Co(BIDPE)2(1,3-bdc)2]n (4)、[Ni(BIDPE)2(1,3-bdc)2]n (5)、 [Ni(IPDPE)2(H2O)2(1,3-bdc)]n (6)、{[Zn(BIDPE)(hdc)]-2H2O}n (7)、 {[Co(BIDPE)(suc)]-3H2O}n (8)、[Co2(BPDPE)2(1,2-bdc)2]n (9)、 [Zn2(BPDPE)2(1,2-bdc)2]n (10)、[Cd2(BPDPE)2(1,2-bdc)2]n (11)、 [Cu2(BPDPE)2(H2O)2(1,2-bdc)2]n (12) [tetrakis(4-pyridyloxymethylene) methane (TPOM), 1,3,5-tris(1-imidazolyl)benzene (tib),1,3-dipyridyl benzene(1,3-dpb), 4,4’-bis(pyridyl) diphenyl ether (BPDPE),4-(pyridyl)-4’-(imidazol-l-yl) diphenyl ether (PIDPE),4,4’-bis(imidazol-l-yl) diphenyl ether (BIDPE), deprotonated 4,4’-dicarboxydiphenylamine (ddpa), deprotonated 1,3-benzenedicarboxylate (1,3-bdc), deprotonated 1,2-benzenedicarboxylate (1,2-bdc), deprotonated Hexanedioic acid (H2hdc), deprotonated Succinic acid (H2suc)]. They were characterized by X-ray single-crystal diffraction, IR spectra, TGA, solid fluorescence spectra and UV-vis spectra.Complex 1 is a 2-fold interpenetrating three-dimensional architecture, topology analysis reveals that the structure can be represented as pcu network topology, complex1 also exhibits good endurance in acid/base aqueous solutions and a high catalytic activity for the reduction of 4-nitrophenol in excess NaBH4 solution. Complex 2 was synthesized with tripodal ligand tib and Cu(NO3)25H2O under solvothermal conditions, exhibits a 3D network due to the existence of O-H-0 interaction, furthermore, complex 2 also has a good catalytic activity for the reduction of 4-nitrophenol in NaBHj solution just like complex 1. Complex 3 crystallizes in the monoclinic system, space group C2/c. The cadmium ion coordinates with three bdc" anions to form 1D ladder-shaped chain.1,3-dpb linked adjacent ID chains to form 3D framework, the whole structure can be symbolized as a pcu topology. Complexes 4 and 5 are isomorphous, exhibit 2D layer networks due to O-H·O hydrogen bonding interactions. Complex 6 is similar to 5 or 6, also exhibits a 2D layer network. Complex 7 reveals 1D double-stranded chains containing [Zn2(BIDPE)2]n and [Zn2(hdc)2]n metallocyclic rings, the adjacent chains are linked by H-bondings and π·π interactions to form 3D network. As a fluorescence material, display a selective sensing of acetone.In complex 8, sue2" anions link Co (Ⅱ) ions to form meso-helical chains, each BIDPE links Co (II) ions to form a zigzag chain, these zigzag and meso-helical chains are linked each other by sharing Co (Ⅱ) ions to generate a 3D framework, meanwhile, the calcination product of complex 8 has a good catalytic activity for the reduction of 4-nitrophenol in NaBH4 solution. Complex 9,10 and 11 are isomorphous, central metal ions link 1,2-bdc to form ID chains, BPDPE link adjacent 1D chains to form 2D network, furthermore, exhibit a 3D network due to interpenetration and π·π interactions.Ini complex 12, Cu (II) ions link BPDPE to form a five-polythreading network,1,2-bdc link the polythreading structures to form a 3D network.In this paper, the structures of 1-12 were studied systematically, meanwhile, the catalytic conversion towards to 4-nitrophenol were studied based on 1,2 and 8, furthermore, the selective sensing of acetone based on 7 was also explored.