American Chemical Society
ja2026807_si_006.cif (33.56 kB)

Molecular Accordion: Vapoluminescence and Molecular Flexibility in the Orange and Green Luminescent Crystals of the Dimer, Au2(μ-bis-(diphenylphosphino)ethane)2Br2

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posted on 2011-07-06, 00:00 authored by Sang Ho Lim, Marilyn M. Olmstead, Alan L. Balch
Solutions containing the components Au+, dppe (dppe is bis(diphenylphosphino)ethane), and Br in a 1:1:1 ratio can produce three different types of crystals: type A, orange luminescent solvates of the dimer Au2(dppe)2Br2 (Au2(μ-dppe)2Br2·2(OSMe2), Au2(μ-dppe)2Br2·2(OCMe2), Au2(μ-dppe)2Br2·2(CH2Cl2), Au2(μ-dppe)2Br2·2(HC(O)NMe2)); type B, green luminescent solvates of the same dimer (Au2(μ-dppe)2Br2·(NCMe) and Au2(μ-dppe)2Br2·0.5(C4H10O)); and type C, orange luminescent solvates of a polymer ({Au(μ-dppe)Br}n·0.5(C4H10O) and {Au(μ-dppe)Br}n·(CH2Cl2)). Some crystals of types A are solvoluminescent. Exposure of type A crystals of Au2(μ-dppe)2Br2·2(OCMe2) or Au2(μ-dppe)2Br2·2(CH2Cl2) to air or vacuum results in the loss of the orange luminescence and the formation of new green luminescent crystals. Subsequent exposure of these crystals to acetone or dichloromethane vapor results in the reformation of crystals of type A. The dimeric complexes in crystals of types A and B are all centrosymmetric and share a common ring conformation. Within these dimers, the coordination geometry of each gold center is planar with a P2Br donor set. In other respects, the Au2(μ-dppe)2Br2 molecule is remarkably flexible and behaves as a molecular accordion, whose dimensions depend upon the solvate content of a particular crystalline phase. In particular, the dimer Au2(μ-dppe)2Br2 is able to accommodate Au···Au separations that range from 3.8479(3) to 3.0943(2) Å, and these variations along with alterations in the Au–Br distances and in the P–Au–P angles are the likely causes of the differences in the luminescence properties of these crystals.