Synthesis, Electrochemical Characterization, and Linear Free Energy Relationship of 1,3-Diphenyl-6-alkyl/arylfulvenes

Document Type

Article

Publication Date

10-21-2016

Publication Title

Journal of Organic Chemistry

Abstract

A series of 1,3-diphenyl-6-alkyl/arylfulvenes was prepared, and the electrochemical properties were investigated. The addition of phenyl groups about the fulvene raised the reduction potential and helped to stabilize the electrochemically generated radical anion. The addition of various functional groups onto the phenyl ring at the 6-position of 1,3,6-triphenylfulvene results in a linear free energy relationship between reduction potential and the Hammett substituent constant, σ. Further extending the conjugation at the 6-position of 1,3-diphenyl-6-arylfulvenes increases the reversibility of the redox reactions, but does not appear to further stabilize the generated radical anion. This in-depth investigation provides evidence that the compounds studied may have utility in light-harvesting applications.

Comments

This work was supported by the Air Force Office of Scientific Research (AFOSR) and the Defense Threat Reduction Agency (DTRA) − Joint Science and Technology Office for Chemical and Biological Defense (MIPR no. HDTRA13964). N.P.G. and S.K.A. were supported through the National Research Council (NRC) Postdoctoral Research Associateship Program.

DOI

10.1021/acs.joc.6b01698

Volume

81

Issue

20

Share

COinS