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Utilization of a Nonemissive Triphosphine Ligand to Construct a Luminescent Gold(I)-Box That Undergoes Mechanochromic
Daniel T Walters1, Reza Babadi Aghakhanpour1, Xian B Powers1
1Department of Chemistry , University of California, Davis , One Shields Avenue , Davis , California 95616 , United States.
Abstract:
Luminescent gold(I) complexes ([Au6(Triphos)4Cl](PF6)5·2(CH3C6H5), [Au6(Triphos)4Cl](AsF6)5·8(CH3C6H5), and [Au6(Triphos)4Cl](SbF6)5·7(CH3C6H5) where Triphos = bis(2-diphenylphosphinoethyl)phenylphosphine) with a boxlike architecture have been prepared and crystallographically characterized. A chloride ion resides at the center of the box with two of the six gold(I) ions nearby. Mechanical grinding of blue luminescent crystals containing the cation, [Au6(Triphos)4Cl]5+, results in their conversion into amorphous solids with green emission that contain the bridged helicate cation, [μ-Cl{Au3(Triphos)2}2]5+. A mechanism of the mechanochromic transformation is proposed. The structures of the blue-emitting helicate, [Au3(Triphos)2](CF3SO3)3·4(CH3C6H5)·H2O, and the green-emitting bridged-helicate, [μ-Cl{Au3(Triphos)2}2](PF6)5·3CH3OH have been determined by single crystal X-ray diffraction.
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