Luminescent Cyclometalated RhIII, IrIII, and (DIP)2RuII Complexes with Carboxylated Bipyridyl Ligands: Synthesis, X-ray Molecular Structure, and Photophysic

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• 作者：Jenny B. Waern ; Christophe Desmarets ; Lise-Marie Chamoreau ; Hani Amouri ; Andrea Barbieri ; Cristiana Sabatini ; Barbara Ventura ; Francesco Barigelletti
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：April 21, 2008
• 年：2008
• 卷：47
• 期：8
• 页码：3340 - 3348
• 全文大小：1340K
• 年卷期：v.47,no.8(April 21, 2008)
• ISSN：1520-510X

文摘

Luminescent cyclometalated rhodium(III) and iridium(III) complexes of the general formula [M(ppy)₂(N^∧N)][PF₆], with N^∧N = Hcmbpy = 4-carboxy-4′-methyl-2,2′-bipyridine and M = Rh (1), Ir (2) and N^∧N = H₂dcbpy = 4,4′-dicarboxy-2,2′-bipyridine and M = Rh (3), Ir (4), were prepared in high yields and fully characterized. The X-ray molecular structure of the monocarboxylic iridium complex [Ir(ppy)₂(Hcmbpy)][PF₆] (2) was also determined. The photophysical properties of these compounds were studied and showed that the photoluminescence of rhodium complexes 1 and 3 and iridium complexes 2 and 4 originates from intraligand charge-transfer (ILCT) and metal-to-ligand charge-transfer/ligand-centered MLCT/LC excited states, respectively. For comparison purposes, the mono- and dicarboxylic acid ruthenium complexes [Ru(DIP)₂(Hcmbpy)][Cl]₂ (5) and [Ru(DIP)₂(H₂dcbpy)][Cl]₂ (6), where DIP = 4,7-diphenyl-1,10-phenanthroline, were also prepared, whose emission is MLCT in nature. Comparison of the photophysical behavior of these rhodium(III), iridium(III), and ruthenium(II) complexes reveals the influence of the carboxylic groups that affect in different ways the ILCT, MLCT, and LC states.