Tailoring of organic dyes with oxidoreductive compounds to obtain photocyclic radical generator systems exhibiting photocatalytic behavior

Beilstein J Org Chem. 2014 Apr 25:10:936-47. doi: 10.3762/bjoc.10.92. eCollection 2014.

Abstract

The combination of a dye which absorbs the photon, an electron acceptor and an electron donor leading to energy conversion through electron transfer, was the basis of the so called three-component systems. In this paper, an experimental work combining Rose bengal dye with a triazine derivative as electron acceptor and ethyl 4-(dimethylamino)benzoate as electron donor, will underline the benefit of the photocyclic behavior of three-component systems leading to the dye regeneration. A thermodynamic approach of the photocycle is presented, followed by a mechanistic and computational study of ideal photocycles, in order to outline the specific kinetics occuring in so called photocatalytic systems. The simple kinetic model used is enough to outline the benefit of the cyclic system and to give the basic requirements in term of chemical combination needed to be fulfilled in order to obtain a photocatalytic behavior.

Keywords: computation; electron transfer; kinetic; photocatalysis; photochemistry; photocyclic initiating system; photopolymerization; photoredox catalysis; radical generator.