Alteration of the Aurophilic Interactions in Trimeric Gold(I) Compounds through Charge Transfer. Behavior of Solvoluminescent Au3(MeNCOMe)3in the Presence of Electron Acceptors

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Abstract
The ability of the triangular gold(I) complex, Au3(MeNCOMe)3, which as a solid displays the novel property of solvoluminescence (see: Vickery, J. C.; Olmstead, M. M.; Fung, E. Y.; Balch, A. L. Angew. Chem., Int. Ed. Engl.1997, 36, 1179) to function as an electron donor has been demonstrated through spectroscopic studies and isolation of crystalline adducts with organic acceptor molecules. Four such adducts with nitro-9-fluorenones have been isolated and subject to single-crystal X-ray diffraction study. These are deep yellow {Au3(MeNCOMe)3}·{2,4,7-trinitro-9-fluorenone}, red {Au3(MeNCOMe)3}·{2,4,5,7-tetranitro-9-fluorenone}, red {Au3(MeNCOEt)3}2·{2,7-dinitro-9-fluorenone}, and red {Au3(MeNCOEt)3}2·{2,4,7-trinitro-9-fluorenone}. The solid-state structures of {Au3(MeNCOMe)3}·{2,4,7-trinitro-9-fluorenone} and {Au3(MeNCOMe)3}·{2,4,5,7-tetranitro-9-fluorenone} consist of columns in which the planar gold(I) trimers and the nearly planar nitro-9-fluorenones are interleaved with the gold trimers making face-to-face contact with the nitroaromatic portion of the electron acceptor. Thus the organic acceptors disrupt the aurophilic interactions present in crystalline {Au3(MeNCOMe)3} itself. However, in {Au3(MeNCOEt)3}2·{2,7-dinitro-9-fluorenone} and {Au3(MeNCOEt)3}2·{2,4,7-trinitro-9-fluorenone}, aurophilic interactions are found which produce dimers, {Au3(MeNCOEt)3}2, with nearly trigonal prismatic Au6 cores. These dimers are interleaved with the nitro-9-fluorenone molecules to again form extended columns in which the components make face-to-face contact. Despite the fact that the gold atoms in {Au3(MeNCOMe)3} and {Au3(MeNCOEt)3} are in exposed sites and only two-coordinate, there is no evidence of additional coordination of the nitro-9-fluorenones with gold centers in the crystalline adducts.

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