Solvent effects on the coexistence of localized and delocalized 4,4'-dinitrotolane radical anion by resonance Raman spectroscopy

Ryan M Hoekstra; João P Telo; Qin Wu; Rachel M Stephenson; Stephen F Nelsen; Jeffrey I Zink

doi:10.1021/ja1017859

Solvent effects on the coexistence of localized and delocalized 4,4'-dinitrotolane radical anion by resonance Raman spectroscopy

J Am Chem Soc. 2010 Jul 7;132(26):8825-7. doi: 10.1021/ja1017859.

Authors

Ryan M Hoekstra¹, João P Telo, Qin Wu, Rachel M Stephenson, Stephen F Nelsen, Jeffrey I Zink

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.

PMID: 20545327
DOI: 10.1021/ja1017859

Abstract

The resonance Raman spectrum of the simple alkyne bridge in 4,4'-dinitrotolane radical anion shows two distinct bands, providing proof of the solvent-dependent coexistence of charge-localized and -delocalized species. The Raman spectra of normal modes primarily involving the charge-bearing -PhNO(2) units also support the coexistence of two solvent-dependent electronic species. The temperature dependence of the spectra of the bridging unit shows an inverse relationship between the solvent reorganization energy (lambda(s)) and the temperature.