Hydrothermal synthesis of copper complexes of 4′-pyridyl terpyridine: From discrete monomer to zigzag chain polymer

• Published in: Inorganica Chimica Acta 2006-09, Vol.359 (12), p.4027-4035
• Main Authors: Feng, Hua, Zhou, Xiao-Ping, Wu, Tao, Li, Dan, Yin, Ye-Gao, Ng, Seik Weng
• Format: Article
• Language: English
• Subjects: Coordination polymer; Copper iodide; Copper mixed-valent complex; Hydrothermal reaction; Terpyridine
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2006.04.035

Several copper-(4′-pyridyl terpyridine) complexes with different nuclearity have been synthesized by one-pot reactions in hydrothermal conditions. By controlling temperature, stoichiometry, reducing agents or solvents, the compounds had been successfully developed from discrete monomers to zigzag polymeric chains with copper oxidation states of monovalence, mixed-valence and divalence. Seven copper complexes [Cu( L1)I 2] ( 1), [Cu 2( L1) 2I 2] 2[Cu 2(μ-I) 2I 2] ( 2), [Cu( L2)I 2] ( 3), [Cu 2( L2)(μ-I)I(PPh 3)] ( 4), [Cu 4( L2) 2(μ-I) 2I 2] ( 5), {[Cu( L2)I] 2[Cu 2(μ-I) 2I 2]} n ( 6) and [Cu 2( L2)(μ-I) 2] n ( 7) have been prepared by reactions of ligands: 4′-(2-pyridyl)-2,2′:6′,2″-terpyridine ( L1) and 4′-(3-pyridyl)-2,2′:6′,2″-terpyridine ( L2) with CuI in hydrothermal conditions, respectively. By alternating the oxidations states of the metal centers, increasing stoichiometric metal/ligand ratio and introducing a second ligand, the compounds, were successfully developed from mononuclear ( 1 and 3) to multinuclear ( 2, 4 and 5) and polymers ( 6 and 7). The synthesis of these compounds may provide an approach for the construction of coordination compounds of 4′-pyridyl terpyridine with different nuclearity.