Highly emissive dinuclear complexes [Au-2{mu-(PPh2)(2)C2B9H10}(C6F5)(PR3)] with different gold fragments coordinated to an anionic diphosphine

作者：Crespo Olga^*; Diez Gil Cesar; Concepcion Gimeno M; Laguna Antonio; Monge Miguel; Ospino Isaura

来源：Dalton Transactions, 2011, 40(39): 10038-10046.

DOI：10.1039/c1dt10890e

Reaction of the yellow-green emitters [Au{(PPh2)(2)C2B9H10}(PR3)] with [Au(C6F5)(tht)] affords orange-red emissive gold complexes [Au-2{mu-(PPh2)(2)C2B9H10}(C6F5)(PR3)] which contain different neutral (PR3) and anionic (C6F5) 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.

• 出版日期2011