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)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."

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2005

Author dc:creator

• Dempsey, Jillian Lee

Advisor dc:contributor.advisor

• Daniel G. Nocera.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/36305

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/36305