Phosphorescent Binuclear Iridium Complexes Based on Terpyridine鈥揅arboxylate: An Experimental and Theoretical Study

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• 作者：Eugen S. Andreiadis ; Daniel Imbert ; Jacques Pe虂caut ; Adrian Calborean ; Ilaria Ciofini ; Carlo Adamo ; Renaud Demadrille ; Marinella Mazzanti
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：September 5, 2011
• 年：2011
• 卷：50
• 期：17
• 页码：8197-8206
• 全文大小：1047K
• 年卷期：v.50,no.17(September 5, 2011)
• ISSN：1520-510X

文摘

The phosphorescent binuclear iridium(III) complexes tetrakis(2-phenylpyridine)渭-(2,2鈥?6鈥?2鈥?terpyridine-6,6鈥?dicarboxylic acid)diiridium (Ir1) and tetrakis(2-(2,4-difluorophenyl) pyridine))渭-(2,2鈥?6鈥?2鈥?terpyridine-6,6鈥?dicarboxylic acid)diiridium (Ir2) were synthesized in a straightforward manner and characterized using X-ray diffraction, NMR, UV鈥搗is absorption, and emission spectroscopy. The complexes have similar solution structures in which the two iridium centers are equivalent. This is further confirmed by the solid state structure of Ir2. The newly reported complexes display intense luminescence in dichloromethane solutions with maxima at 538 (Ir1) and 477 nm (Ir2) at 298 K (496 and 468 nm at 77 K, respectively) and emission quantum yields reaching 18% for Ir1. The emission quantum yield for Ir1 is among the highest values reported for dinuclear iridium complexes. It shows only a 11% decrease with respect to the emission quantum yield reported for its mononuclear analogue, while the molar extinction coefficient is roughly doubled. This suggests that such architectures are of potential interest for the development of polymetallic assemblies showing improved optical properties. DFT and time-dependent-DFT calculations were performed on the ground and excited states of the complexes to provide insights into their structural, electronic, and photophysical properties.