| In this paper,18 new functional coordination polymers were successfully constructed by adjusting the ductility of ligands and carboxylic acid ligands.The selected bis-pyridine-bis-amide ligands with semi-rigid thiophene subunits are N,N'-bis(4-methylenepyridyl)-2,5-thienodicarbonamide(4-bmptd)and N,N'-bis(3-methylenepyridyl)-2,5-thienodicarbonamide(3-bmptd),while the bis-pyridine-bis-amide ligands with flexible carbon chain spacers are N,N'-di(3-pyridinecarboxamide)-1,4-butane(3-dpyb),N,N'-di(3-pyridinecarboxamide)-1,6-hexane(3-dpyh)and N,N'-di(4-pyridinecarboxamide)-1,6-hexane(4-dpyh),and four organic polycarboxylic acids [5-hydroxylisophthalic acid(5-H2HIP),5-nitroisophthalic acid(5-H2NIP).5-methylisophthalic acid(5-H2MIP),isophthalic acid(H2IPA)] and one tetracarboxylic acid [3-(3',5'-dicarboxylphenoxy)phthalic acid(H4dcppa)] as co-ligands,and four transition metals with different electron configurations,Zn/Cd/Co/Ni,were self-assembled under hydrothermal conditions of 120 ?.These complexes were characterized by single crystal X-ray diffraction(XRD),infrared spectroscopy(IR)and powder X-ray diffraction(PXRD),and their electrochemical/electrocatalytic behavior and fluorescence sensing properties were also investigated according to the properties of the metals and ligands.1.Four Co complexes,four Ni complexes and three Cd complexes were synthesized with Co/Ni/Cd under the hydrothermal condition of 120 ?,using the semi-rigid thiophene-briged bis-pyridine-bis-amide ligands with different pyridine N sites(4-bmptd and 3-bmptd)and four dicarboxylic acids(5-H2 HIP,5-H2 NIP.5-H2 MIP and H2IPA)as co-ligands.The influence of the choice of carboxylic acid with different types on the structure of the complex was discussed.In addition,its electrocatalytic and fluorescence properties were investigated.[Co(4-bmptd)(5-HIP)(H2O)2]·2H2O(1)[Co(4-bmptd)(5-NIP)](2)[Co(4-bmptd)(5-MIP)](3)[Co(4-bmptd)(IPA)(H2O)](4)[Ni(4-bmptd)(5-HIP)(H2O)2]·2H2O(5)[Ni(4-bmptd)(5-NIP)](6)[Ni(4-bmptd)(5-MIP)](7)[Ni2(4-bmptd)2(IPA)2(H2O)2]·2H2O(8)[Cd(3-bmptd)(5-HIP)(H2O)](9)[Cd(3-bmptd)(5-NIP)(H2O)](10)[Cd(3-bmptd)(IPA)]·H2O(11)Complexes 1 and 5 are isomorphic and show a 2D interpenetrating structure.Complexes 2 and 6 are isomorphic,both of which are two-layer planar structures.Complexes 3 and 7 are isomorphic,that also have a double planar structure.Complex 4 has a wavy 2D structure and 8 has a planar 2D structure.Complex 9 is a twisted wavy 2D structure.Complex 10 is a twisted wavy two-layer 2D structure.Complex 11 is a 3D framework.2.Considering the flexibility of the ligands,bis-pyridine-bis-amide ligands bridged by flexible carbon chains' spacers(3-dpyb,3-dpyh,4-dpyh)and tetraparboxylic acid(H4dcppa)were selected as co-ligands,and self-assembled with the transition metal(Zn/Cd/Co)under hydrothermal conditions of 120 ?.Fluorescence and electrocatalysis properties were also investigated.In addition,the magnetic susceptibility of 18 was also tested preliminarily.[Zn2(3-dpyb)0.5(dcppa)(H2O)3]·2H2O(12)[Cd2(3-dpyb)0.5(dcppa)(H2O)](13)[Zn2(3-dpyh)0.5(dcppa)(H2O)3]·2H2O(14)[Cd2(3-dpyh)0.5(dcppa)(H2O)3]·H2O(15)[Co2(3-dpyb)0.5(dcppa)(H2O)3]·2H2O(16)[Co2(3-dpyh)0.5(dcppa)(H2O)3]·2H2O(17)[Co5(?3-OH)2(4-dpyh)(dcppa)2(H2O)2]·2H2O(18)Complexes 12 and 16 are isomorphic,both of which are binuclear metal cluster 3D structures.Complex 13 is a tanglesome 3D structure based on tetra-nuclear Cd clusters.Complexes 14 and 17 are isomorphic,both of which are 3D frame configurations based on binuclear metal clusters.Complex 15 is a 3D structure based on bi-nuclear Cd cluster.Complex 18 is an interesting 3D structure with penta-nuclear Co cluster. |
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