| In this work,two semi-rigid bis-pyridyl-bis-amide ligands with different conjugate volume N,N?-bis?4-methylenepyridin-4-yl?-1,4-benzenedicarboxamide?4-bmbpd?and N,N?-bis?4-methylenepyridin-4-yl?-2,6-naphthalenedicarboxamide?4-bmnpd?were selected as the main ligands,and different polycarboxylates[1,4-benzenedicarboxylic acid?1,4-H2BDC?,4,4'-oxybisbenzoic acid?H2OBA?,2,2'-biphenyldicarboxylic acid?2,2?-H2BDC?,5-aminoisophthalic acid?5-H2AIP?,2,5-thiophenedicarboxylic acid?H2TPD?,1,3-benzenedicarboxylic acid?1,3-H2BDC?,5-methylisophthalic acid?5-H2MIP?,5-nitroisophthalic acid?5-H2NIP?,2,5-pyridinedicarboxylic acid?2,5-H2TPD?,3-nitrophthalic acid?3-H2NIP?,5-hydroxyisophthalicacid?5-H2HIP?and 1,3,5-benzenetricarboxylic acid?1,3,5-H3BTC?] have been used as the auxiliary ligands to constructure coordination polymers with transition metal atoms under hydrothermal conditions.Seventeen new complexes have been synthesized and structurally characterized by single-crystal X-ray diffraction analyses,IR spectra and powder X-ray diffraction?PXRD?The TG,electrochemical behaviors,fluorescent behaviors,and photocatalytic activities of some coordination polymers have been investigated.1.Using a semi-rigid bis-pyridyl-bis-amide with 1,4-benzene bridge?4-bmbpd?as main ligand and multiply polycarboxylates as auxiliary ligands,fourteen transition metals complexes with different structural features have been synthesized under hydrothermal conditions and structurally characterized.The influence of the 4-bmbpd ligand,polycarboxylates auxiliary ligands and the central metals on the structures of complexes has been studyed.[Co?4-bmbpd??1,4-BDC??H2O?2]·2H2O?1?[Co?4-bmbpd??OBA?]·H2O?2?[Co?4-bmbpd??2,2?-BDC?]·H2O?3?[Co?4-bmbpd??5-NIP?]·2H2O?4?[Co?4-bmbpd?0.5?5-AIP?]·H2O?5?[Co3?4-bmbpd?3?1,3,5-BTC?2?H2O?4]·4H2O?6?[Ni?4-bmbpd??H2O?4]·?TPD??7?[Ni2?4-bmbpd?2?1,3-BDC?2?H2O?4]·5H2O?8?[Ni2?4-bmbpd?2?MIP?2?H2O?2]·3H2O?9?[Ni3?4-bmbpd?3?BTC?2?H2O?4]·4H2O?10?[Zn3?4-bmbpd?2?1,4-BDC?3]?11?[Zn?4-bmbpd??4,4?-OBA?]·H2O?12?[Zn3?4-bmbpd?1.5?2,2?-BDC?3]?13?[Zn?4-bmbpd??1,3,5-HBTC?]·2H2O?14?Single crystal X-ray diffraction analysis reveals that complexes 1-14 show different structures from 1D to 3D.Alought Complexes 1-3?8?9 and11-13 show similar 2D network,they are different from each other due to different polycarboxylates auxiliary ligands.It is noted that the 4-bmbpd ligand adopts a ?1-coordination mode hanging on both sides of the 2D layer in11,and one pyridyl nitrogen atom from 4-bmbpd molecule is uncoordination.Complexes 4 and 7 are both 1D structures.4 is a 1D tubular structure with38-membered [Co2?4-bmbpd2?] loop and 7 is a 1D wave-liked chains.Complexes 5 ? 6 ? 10 and 14 display three defferent 3D frameworks.5 a4,5-connected 3D network with the point symbol of {44·62}{44·66}.The finally structure of 6 and 10 is similar and the structure can be described as a?2,3,4,4?-connected framework,furthermore,two identical frameworks interpenetrate each other creating a 2-fold interpenetrating framework.The3 D framework of 14 is a threefold interpenetrated framework,which possess4-connected diamond network,it should be noted that the third carboxyl group of the 1,3,5-HBTC was protonated and uncoordinated.It is suggest that the coordination mode of organic polycarboxylates and main ligands play an important role in the construction of final frameworks.The TG,electrochemical behaviors,fluorescent behaviors,and photocatalytic activities of some coordination polymers have been investigated.2.By changing the N-donor ligand with different conjugate volume,semi-rigid bis-pyridyl-bis-amide with 2,6-Naphthalene bridge?4-bmnpd?as main ligand,three Cd II complexes with different structural features have been hydrothermally synthesized and structurally characterized.The influence of organic polycarboxylates on the structures and performances of these complexes has been investigated.[Cd?4-bmnpd?0.5?5–MIP??H2O?]?15?[Cd?4-bmnpd??5–HIP??H2O?]?16?[Cd?4-bmnpd??3–NIP??H2O?]?17?Complexes 15-17 are both 2D network with different coordination features.Complex 15 is a 2D stair-like network and the semi-rigid bis-pyridyl-bis-amide ligand adopts a ?4-bridging mode in 15?via ligation of two amide oxygen atoms and two pyridyl nitrogen atoms?.Complex 16 is also2 D network which possess 1D [Cd-4-bmnpd]n meso-spiral chain.In 17,Cd ions linked by two 3-NIP auxiliary ligands to form [Cd2NIP2] unit,furthermore,the unit linked by 1D [Cd-4-bmnpd]n wave-like chains to create2 D network.It is suggest that the organic polycarboxylates play an important role in the construction of final frameworks.Furthermore,the photoluminescent sensing behavior of 15 and 16 for Fe3+ ions have been investigated. |
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