Metal/Carboxylate-Induced Versatile Structures of Nine 0D → 3D Complexes with Different Fluorescent and Electrochemical Behaviors.

To investigate the effect of the polycarboxylates and metal ions on the assembly and structures of complexes based on a thiophene-containing bis-pyridyl-bis-amide ,-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide (3-bptpa) ligand, nine 0D → 3D complexes of [Ni(3-bptpa)(1,2-BDC)(HO)] (), [Ni(3-bptpa)(IP)(HO)]·HO (), [Ni(3-bptpa)(5-MIP)(HO)]·HO (), [Ni(3-bptpa)(5-NIP)(HO)] (), [Ni(3-bptpa)(5-AIP)]·2HO (), [Ni(OH)(3-bptpa)(1,3,5-BTC)]·DMA·5HO (), [Cu(3-bptpa)(5-MIP)]·3HO (), [Cu(3-bptpa)(5-AIP)(HO)]·HO (), and [Cu(3-bptpa)(1,3,5-HBTC)] () (1,2-HBDC = 1,2-benzenedicarboxylic acid, HIP = 1,3-benzenedicarboxylic acid, 5-HMIP = 5-methylisophthalic acid, 5-HNIP = 5-nitroisophthalic acid, 5-HAIP = 5-aminoisophthalic acid, DMA = ,'-dimethylacetamide, and 1,3,5-HBTC = 1,3,5-benzenetricarboxylic acid) have been hydrothermally/solvothermally synthesized and structurally characterized by IR, thermogravimetric, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex is a zero-dimensional (0D) bimetallic complex. Complexes and feature two similar one-dimensional ladderlike structures. Complex displays a two-dimensional (2D) 4-connected network based on single-metallic nodes. Complex shows a 2D double-layer structure containing a pair of 6 [Ni(5-AIP)] honeycomblike sheets. Complex is a 3,5-connected three-dimensional (3D) framework derived from bimetallic nodes and 6 [Ni(OH)(1,3,5-BTC)] honeycomblike sheets. Complex displays a 2D 4-connected grid based on bimetallic nodes. Complex features a 2D double-layer structure based on two 4-connected [Cu(3-bptpa)(5-AIP)] sheets and bridging coordinated water molecules. Complex is a 2D structure extended by incomplete deprotonation of 1,3,5-HBTC and 3-bptpa linkers. The effect of the metal ions and polycarboxylates on the structures of the title complexes was discussed, and the fluorescent properties of - were investigated. The carbon paste electrodes bulk-modified by complexes , , and - show different electrocatalytic activities for the oxidation of ascorbic acid as well as the reduction of hydrogen peroxide, nitrites, and bromates.