Synthesis, structure and spectroscopic investigations of luminescent heterobimetallic gold(I)-Rhodium(I) species
Author(s)Dempsey, Jillian Lee
Massachusetts Institute of Technology. Dept. of Chemistry.
Daniel G. Nocera.
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A novel, three-coordinate gold(I) dimer, Au2(tfepm)3Cl2 (la, lb), was synthesized and structurally characterized. Four gold(I)-rhodium(I) heterobimetallic complexes, AuIRh'(tBuNC)2(-dppm)2C12 (2), Au'Rh'(tBuNC)2(u-dmpm)2Cl2 (3), Au'Rh'(tBuNC)2(,u-tfepm)2C12 (4), and AuIRh(tBuNC)2(u-tfepma)2Cl2 (5) were synthesized and 2, 3, and 5 were crystallographically characterized. Absorption spectra at room temperature, excitation spectra, emission spectra, and phosphorescence lifetimes of glass-solution and solid state samples at 77 K are reported for 2-5 and interpreted in context of crystallographic structure, electronic structure, and time-dependent density functional theory (TD-DFT) calculations. 2-5 are intensely luminescent at 77 K, with 4 and 5 exhibiting "dual emission."
Thesis (S.B.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005.Some images on CDROM are in colour.Includes bibliographical references (leaves 33-34, first group).
DepartmentMassachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology