Title

Dihedral-Angle-Controlled Crossover from Static Hole Delocalization to Dynamic Hopping in Biaryl Cation Radicals

Document Type

Article

Language

eng

Publication Date

11-29-2016

Publisher

Wiley-VCH Verlag

Source Publication

Angewandte Chemie International Edition

Source ISSN

1433-7851

Original Item ID

10.1002/anie.201609695

Abstract

In cases of coherent charge-transfer mechanism in biaryl compounds the rates follow a squared cosine trend with varying dihedral angle. Herein we demonstrate using a series of biaryl cation radicals with varying dihedral angles that the hole stabilization shows two different regimes where the mechanism of the hole stabilization switches over from (static) delocalization over both aryl rings to (dynamic) hopping. The experimental data and DFT calculations of biaryls with different dihedral angles unequivocally support that a crossover from delocalization to hopping occurs at a unique dihedral angle where the electronic coupling (Hab) is one half of reorganization (λ), that is, Hab=λ/2. The implication of this finding in non-coherent charge-transfer rates is being investigated.

Comments

Dihedral-Angle-Controlled Crossover from Static Hole Delocalization to Dynamic Hopping in Biaryl Cation Radicals, Vol. 56, No. 1 (November 29, 2016): 266-269. DOI.