A rational design of metallomacrocyclic complexes with superior π acidity and bacisity vs. organic counterparts: Inorganic rules!

INOR 645

Sammer M. Tekarli, stekarli@yahoo.com, Thomas R. Cundari, tomc@unt.edu, and Mohammad A. Omary, omary@unt.edu. Department of Chemistry, University of North Texas, Box 305070, Denton, TX 76203
Density functional theory (DFT) has been used to assess the π acidity and basicity of inorganic trimetallic macromolecular complexes of the type [M(µ-L)]3 where M = Cu, Ag, or Au and L = carbeniate, imidazolate, pyridiniate, pyrazolate, and triazolate. The organic compounds benzene, triazole, and pyridine were also modeled and their substituents effects were compared to the inorganics. Our results, based on molecular electrostatic potential surfaces and binding energies, indicate that the inorganic macromolecules show superior π acidity and basicity compared to the analogous organic counterparts. Moreover, the inorganic cyclic trimers are found to exhibit acidity and bacisity that can be systematically tuned by judicious variation of the metal (relative π basicity: Au > Cu > Ag) and the bridging ligand (relative π basicity: imidazolate > pyridiniate > carbeniate > pyrazolate > triazolate), in addition to substituent (inductive) effects. These computational findings are inspiring experimental efforts to design novel binary materials exhibiting interesting optoelectronic properties, such as molecular light-emitting diodes and new classes of solid-state conductors and semiconductors.
 

Computational Chemistry
7:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006