INOR 240 |
| Young-A Lee1, Quan-Ming Wang1, Joseph Deaton2, Henry J. Gysling2, and Richard Eisenberg1. (1) Department of Chemistry, University of Rochester, Rochester, NY 14627-0216, (2) Research Laboratories, Eastman Kodak Company, Rochester, NY 14650-2109 |
| Interest in gold(I) complexes has been stimulated by their tendency to aggregate through closed shell "aurophilic" interactions and their consequent structural and luminescence properties. New studies on two series of Au(I) compounds will be described. The first series has the general formula [(m3-E)Au3Ag(m-PPh2py)3]2+ where E=O, S, Se. These heterobimetallic complexes have been characterized structurally and exhibit bright solid state luminescence at 298 K that differs with E (blue for O; yellow for S; orange-red for Se), leading to a tentative 3LMMCT excited state assignment. The second series of complexes are new binuclear Au(I) systems containing bridging bis(diphenylphosphino)methane and thiouracilate ligands. These systems exhibit unique luminescence tribochromism in the solid state in which photo-emission turns on upon gentle crushing of the sample to give a bright cyan emission when irradiated at 375 nm. The non-emissive form of these complexes has an extended helical ...Au...Au...Au ... structure in the solid with weak aurophilic interactions, whereas the cyan emissive form has strong intermolecular aurophilic interactions that lead to an arrangement of dimers of the binuclear (Au2) complexes in the solid state. The conversion from non-emissive to emissive form occurs with release of acid and recrystallization of the latter in the presence of acid regenerates the non-emissive form. |
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Contemporary Aspects of Chemical Bonding
8:40 AM-12:00 PM, Monday, September 8, 2003 Javits Convention Center -- 1A26/1A27, Oral
Division of Inorganic Chemistry |