Assembly of Multitrack Cu−N Coordination Polymeric Chain-Modified Polyoxometalates Influenced by Polyoxoanion Cluster and Ligand

• Published in: Crystal growth & design Vol. 7; no. 12; pp. 2535 - 2541
• Main Authors: Sha, Jingquan, Peng, Jun, Tian, Aixiang, Liu, Hongsheng, Chen, Jing, Zhang, Pengpeng, Su, Zhongmin
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 01.12.2007
• Subjects: Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Growth from solutions; Materials science; Methods of crystal growth; physics of crystal growth; Organic compounds; Other materials; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Metallates; Stacking sequence; Organometallic compounds; Ethylene; Bipyridines; XRD; Monocrystals; Electrochemical properties; Hydrothermal synthesis; Crystal growth from solutions; Ligands; Copper complexes; Crystal structure
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg070438b

By introducing different long rigid ligands into polyoxometalate (POM) systems, four novel inorganic–organic hybrids containing multitrack Cu−N coordination polymeric chain-modified POMs, {[Cu(4,4′-bipy)]3[HGeMo12O40]}·0.5H2O (1), [Cu(4,4′-bipy)]{[Cu(4,4′-bipy)]2[W6O19]}·4H2O (2) (bipy = bipyridine), [Cu(bpe)]{[Cu(bpe)]2[GeMo12O40(VO)2]} (3) (bpe = bis(4-pyridyl)ethylene), and [Cu2(phnz)3]2[SiW12O40] (4) (phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods. The crystal structures of 1–4 have been established by single crystal X-ray diffraction. Compound 1 exhibits a tritrack Cu−N chain-modified Keggin POM 1D structure. Compound 2 represents the first example of a 2D framework constructed from a Lindquist polyoxoanion modified by double bitrack Cu−N chains via its terminal oxygen and bridge oxygen atoms. The rail-like 1D structure of compound 3 is formed from Keggin clusters modified by double monotrack Cu−N chains. Compound 4 shows a pseudo-1D structure of double monotrack Cu−N chain-modified Keggin POMs through offset face-to-face π−π stacking interactions between the adjacent phnz molecules. Investigation of their structural differences shows the important roles of the size of POMs and the unit length of the Cu−N chains in the assembly process of the solid structures. Furthermore, the electrochemical properties of 1−4 were studied.