Osawa Masahisa, Hashimoto Masashi, Kawata Isao, Hoshino Mikio
Luminescent Materials Laboratory, RIKEN, 2-1 Hirosawa, Wako-Shi 351-0198, Japan.
Dalton Trans. 2017 Sep 26;46(37):12446-12455. doi: 10.1039/c7dt02460f.
Synthesis and X-ray structures of silver(i) bromide complexes with diphosphine ligands L, L, and L are described, where L = 1,2-bis[bis(2-methylphenyl)phosphino]benzene, L = 1,2-bis[bis(2-ethylphenyl)phosphino]benzene, and L = 1,2-bis[bis(2-isopropylphenyl)phosphino]benzene. Crystals of complex [(L)AgBr] (1), prepared from L and AgBr, showed a tetrahedral bimetallic structure. L and L, with bulkier substituents than those of L, reacted with AgBr to give crystalline three-coordinate complexes (L)AgBr (2) and (L)AgBr (3). Nuclear magnetic resonance (NMR) studies demonstrated that 1 dissociates in solution to yield a monomeric three-coordinate complex (L)AgBr. Luminescence studies showed that complexes 1-3 exhibit efficient blue thermally activated delayed fluorescence (TADF) in both solid state and solution. Density functional theory (DFT)/Time-dependent (TD)-DFT calculations revealed that the electronic transition responsible for TADF corresponds to (σ + Br) → π*. The photophysical properties of silver complexes 1-3 are discussed in detail and compared to those of the copper complex (L)CuBr.
描述了溴化银（I）与二膦配体L、L和L形成的配合物的合成及X射线结构，其中L = 1,2 - 双[双（2 - 甲基苯基）膦基]苯，L = 1,2 - 双[双（2 - 乙基苯基）膦基]苯，L = 1,2 - 双[双（2 - 异丙基苯基）膦基]苯。由L和AgBr制备的配合物[(L)AgBr]（1）的晶体呈现四面体双金属结构。L和L具有比L更大的取代基，它们与AgBr反应生成晶体三配位配合物（L）AgBr（2）和（L）AgBr（3）。核磁共振（NMR）研究表明，1在溶液中解离生成单体三配位配合物（L）AgBr。发光研究表明，配合物1 - 3在固态和溶液中均表现出高效的蓝色热激活延迟荧光（TADF）。密度泛函理论（DFT）/含时（TD）- DFT计算表明，负责TADF的电子跃迁对应于（σ + Br）→π*。详细讨论了银配合物1 - 3的光物理性质，并与铜配合物（L）CuBr的光物理性质进行了比较。
