Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA/UJF-Grenoble 1, INAC, Grenoble, F-38054, France.
Inorg Chem. 2011 Sep 5;50(17):8197-206. doi: 10.1021/ic200704s. Epub 2011 Aug 10.
The phosphorescent binuclear iridium(III) complexes tetrakis(2-phenylpyridine)μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir1) and tetrakis(2-(2,4-difluorophenyl) pyridine))μ-(2,2':6',2''-terpyridine-6,6''-dicarboxylic acid)diiridium (Ir2) were synthesized in a straightforward manner and characterized using X-ray diffraction, NMR, UV-vis 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.
具有磷光的双核铱(III)配合物四(2-苯基吡啶)μ-(2,2':6',2''-三联吡啶-6,6''-二羧酸)二铱(Ir1)和四(2-(2,4-二氟苯基)吡啶))μ-(2,2':6',2''-三联吡啶-6,6''-二羧酸)二铱(Ir2)以简单的方式合成，并通过 X 射线衍射、NMR、UV-vis 吸收和发射光谱进行了表征。该配合物具有相似的溶液结构，其中两个铱中心是等价的。这进一步通过 Ir2 的固态结构得到证实。新报道的配合物在二氯甲烷溶液中显示出强烈的发光，在 298 K 时最大发射波长分别为 538nm(Ir1)和 477nm(Ir2)(468nm 在 77K 时，分别为 496nm)，发射量子产率达到~18%对于 Ir1。Ir1 的发射量子产率是双核铱配合物中报道的最高值之一。与单核类似物的发射量子产率相比，它仅下降了 11%，而摩尔消光系数大致增加了一倍。这表明此类结构对于开发具有改进光学性质的多金属组装体具有潜在的兴趣。对配合物的基态和激发态进行了密度泛函理论和含时密度泛函理论计算，以深入了解其结构、电子和光物理性质。
