Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, Pedro Cerbuna 12, 50009, Zaragoza, Spain.
Dalton Trans. 2011 Oct 21;40(39):10038-46. doi: 10.1039/c1dt10890e. Epub 2011 Sep 9.
Reaction of the yellow-green emitters [Au{(PPh(2))(2)C(2)B(9)H(10)}(PR(3))] with [Au(C(6)F(5))(tht)] affords orange-red emissive gold complexes [Au(2){μ-(PPh(2))(2)C(2)B(9)H(10)}(C(6)F(5))(PR(3))] which contain different neutral (PR(3)) and anionic (C(6)F(5)) auxiliary ligands and an anionic diphosphine. The resulting complexes are among the few reported in which an ortho-carborane diphosphine acts in a bridging mode, and are unique in containing not a closo- (neutral), but a nido-carborane (anionic) cluster. DFT and TDDFT calculations led to the prediction of the origin of the two first singlet-triplet transitions, which is consistent with the experimental results. Although the blue emissive nido-diphosphine plays a key role in the transitions of the three-coordinate precursors and the final dinuclear complexes, it is the environment around the gold centre that controls the emission energy.
黄色-绿色发射器[Au{(PPh(2))(2)C(2)B(9)H(10)}(PR(3))]与[Au(C(6)F(5))(tht)]反应生成橙色-红色发射性金配合物[Au(2){μ-(PPh(2))(2)C(2)B(9)H(10)}(C(6)F(5))(PR(3))]，其中包含不同的中性(PR(3))和阴离子(C(6)F(5))辅助配体和阴离子二膦。所得到的配合物是少数报道的其中一个邻位-碳硼烷二膦以桥接模式作用的配合物之一，并且是独特的，因为它含有不是闭式（中性），而是开式（阴离子）碳硼烷簇。DFT 和 TDDFT 计算导致了两个第一单重态-三重态跃迁的起源的预测，这与实验结果一致。虽然蓝色发射性开式二膦在三配位前体和最终双核配合物的跃迁中起着关键作用，但控制发射能量的是金中心周围的环境。
