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

Guo-Cheng Liu; Xue Lu; Xiao-Wu Li; Xiu-Li Wang; Na Xu; Yan Li; Hong-Yan Lin; Yong-Qiang Chen

doi:10.1021/acsomega.9b02124

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

ACS Omega. 2019 Oct 8;4(17):17366-17378. doi: 10.1021/acsomega.9b02124. eCollection 2019 Oct 22.

Authors

Guo-Cheng Liu^{1

2}, Xue Lu¹, Xiao-Wu Li², Xiu-Li Wang¹, Na Xu¹, Yan Li¹, Hong-Yan Lin¹, Yong-Qiang Chen³

Affiliations

¹ Faculty of Chemistry and Chemical Engineering, Liaoning Province Silicon Materials Engineering Technology Research Centre, Bohai University, Jinzhou 121013, P. R. China.
² Department of Materials Physics and Chemistry, School of Materials Science and Engineering, and Key Laboratory for Anisotropy and Texture of Materials, Ministry of Education, Northeastern University, Shenyang 110819, P. R. China.
³ College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong, Shanxi 030619, P. R. China.

Abstract

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 N,N'-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide (3-bptpa) ligand, nine 0D → 3D complexes of [Ni₂(3-bptpa)₄(1,2-BDC)₂(H₂O)₂] (1), [Ni(3-bptpa)(IP)(H₂O)₂]·H₂O (2), [Ni(3-bptpa)(5-MIP)(H₂O)₂]·H₂O (3), [Ni(3-bptpa)(5-NIP)(H₂O)] (4), [Ni(3-bptpa)(5-AIP)]·2H₂O (5), [Ni₂(OH)(3-bptpa)(1,3,5-BTC)]·DMA·5H₂O (6), [Cu(3-bptpa)(5-MIP)]·3H₂O (7), [Cu(3-bptpa)(5-AIP)(H₂O)_0.25]·H₂O (8), and [Cu(3-bptpa)(1,3,5-HBTC)] (9) (1,2-H₂BDC = 1,2-benzenedicarboxylic acid, H₂IP = 1,3-benzenedicarboxylic acid, 5-H₂MIP = 5-methylisophthalic acid, 5-H₂NIP = 5-nitroisophthalic acid, 5-H₂AIP = 5-aminoisophthalic acid, DMA = N,N'-dimethylacetamide, and 1,3,5-H₃BTC = 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 1 is a zero-dimensional (0D) bimetallic complex. Complexes 2 and 3 feature two similar one-dimensional ladderlike structures. Complex 4 displays a two-dimensional (2D) 4-connected network based on single-metallic nodes. Complex 5 shows a 2D double-layer structure containing a pair of 6³ [Ni(5-AIP)] honeycomblike sheets. Complex 6 is a 3,5-connected three-dimensional (3D) framework derived from bimetallic nodes and 6³ [Ni₂(OH)(1,3,5-BTC)] honeycomblike sheets. Complex 7 displays a 2D 4-connected grid based on bimetallic nodes. Complex 8 features a 2D double-layer structure based on two 4-connected [Cu(3-bptpa)(5-AIP)] sheets and bridging coordinated water molecules. Complex 9 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 1-9 were investigated. The carbon paste electrodes bulk-modified by complexes 3, 5, and 6-9 show different electrocatalytic activities for the oxidation of ascorbic acid as well as the reduction of hydrogen peroxide, nitrites, and bromates.