ja8b01666_si_003.cif (2.42 MB)

Utilization of a Nonemissive Triphosphine Ligand to Construct a Luminescent Gold(I)-Box That Undergoes Mechanochromic Collapse into a Helical Complex

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posted on 30.04.2018, 00:00 by Daniel T. Walters, Reza Babadi Aghakhanpour, Xian B. Powers, Kamran B. Ghiassi, Marilyn M. Olmstead, Alan L. Balch
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.