Crespo Olga, Gimeno M Concepción, Jones Peter G, Laguna Antonio, López-de-Luzuriaga José M, Monge Miguel, Pérez Juan L, Ramón Miguel A
Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain.
Inorg Chem. 2003 Mar 24;42(6):2061-8. doi: 10.1021/ic0259843.
The free nido-diphosphine anions (PR(2))(2)C(2)B(9)H(10) (R = Ph, (i)Pr) show luminescence properties whereas the closo-diphosphines [(PR(2))(2)C(2)B(10)H(10)] do not. Four families of three-coordinate complexes of stoichiometry [Au[(PR(2))(2)C(2)B(10)H(10)]L]OTf (L = tertiary phosphine) and [Au[(PR(2))(2)C(2)B(9)H(10)]L] have been studied in order to analyze the influence of the closo- or nido-nature of the diphosphine, the monophosphine coordinated to gold and the substituent at the diphosphine on the luminescence of the complexes. Only the nido-derivatives show luminescence. The maxima of the emissions are shifted to lower energies than those of the corresponding free nido-diphosphines. When the substituent at the diphosphine is phenyl, a new emission appears, which has been assigned as arising from a metal to ligand charge transfer [Au-->pi(L)] excited state.
自由的巢式二膦阴离子(PR(2))(2)C(2)B(9)H(10)（R = Ph，(i)Pr）具有发光性质，而闭式二膦[(PR(2))(2)C(2)B(10)H(10)]则没有。为了分析二膦的闭式或巢式性质、与金配位的单膦以及二膦上的取代基对配合物发光的影响，研究了化学计量比为[Au[(PR(2))(2)C(2)B(10)H(10)]L]OTf（L = 叔膦）和[Au[(PR(2))(2)C(2)B(9)H(10)]L]的四类三配位配合物。只有巢式衍生物显示出发光。发射的最大值比相应的自由巢式二膦的发射最大值向更低能量移动。当二膦上的取代基为苯基时，会出现一种新的发射，它被认为是由金属到配体的电荷转移[Au-->pi(L)]激发态产生的。
