Synthesis, Structure and Spectroscopic Investigations of Luminescent Heterobimetallic Gold(I)-Rhodium(I) Species

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) 2Cl 2 (3), Au'Rh'( tBuNC) 2(,utfepm)2 C12 (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 Supervisor: Daniel G. Nocera