Issue 4, 2010

A case study of the ZnII-BDC/bpt mixed-ligand system: positional isomeric effect, structural diversification and luminescent properties

Abstract

To systematically investigate the influence of the positional isomeric ligands on the structures and properties of transition metal complexes, we synthesized eight Zn(II) complexes with three positional isomeric carboxylate ligands (p-BDC, m-BDC and o-BDC) and three positional isomeric dipyridyl bridging ligands (4,4′-bpt, 3,4′-bpt and 3,3′-bpt). {[Zn2(p-BDC)2(4,4′-bpt)2]·H2O·(C2H5OH)}n (1), {[Zn(p-BDC)(3,4′-bpt)2(H2O)2]·2H2O}n (2), {[Zn(p-BDC)(3,3′-bpt)2(H2O)2]·3H2O}n (3), {[Zn2(m-BDC)2(4,4′-bpt)(H2O)3]·H2O}n (4), [Zn(m-BDC)(3,4′-bpt)]n (5), {[Zn(m-BDC)(3,3′-bpt)]·H2O}n (6), [Zn(o-BDC)(4,4′-bpt)]n (7) and [Zn2(o-BDC)2(3,4′-bpt)]n (8) (p-BDC = 1,4-benzenedicarboxylate anion, m-BDC =1,3-benzenedicarboxylate anion, o-BDC = 1,2-benzenedicarboxylate anion, 4,4′-bpt = 1H-3,5-bis(4-pyridyl)-1,2,4-triazole, 3,4′-bpt = 1H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole and 3,3′-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-triazole). Structural analysis reveals that the benzenedicarboxylate isomers display versatile coordination modes to manage the Zn(II) ions to form 1D chains (for 2–5, 7 and 8) or 2D layers (for 1 and 6), which are further extended via the isomeric bpt connectors in different directions to give rise to a variety of coordination polymers, such as 1D decorated chain, 1D ladder-like chain, 2D sql layer, 2D bilayer with 82·10 topology, 2D wave-like layer, 3D 2-fold interpenetrating porous pcu net and 3D CsCl net. These results indicate that the nature of isomeric benzenedicarboxylates and bpt ligands has an important effect on the structural topologies of such Zn(II) complexes. Moreover, the luminescent properties of the complexes have been briefly investigated.

Graphical abstract: A case study of the ZnII-BDC/bpt mixed-ligand system: positional isomeric effect, structural diversification and luminescent properties

Supplementary files

Article information

Article type
Paper
Submitted
29 Jul 2009
Accepted
16 Nov 2009
First published
17 Dec 2009

CrystEngComm, 2010,12, 1269-1279

A case study of the ZnII-BDC/bpt mixed-ligand system: positional isomeric effect, structural diversification and luminescent properties

F. Huang, J. Tian, G. Chen, D. Li, W. Gu, X. Liu, S. Yan, D. Liao and P. Cheng, CrystEngComm, 2010, 12, 1269 DOI: 10.1039/B915506F

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