Correlations Between Excited-State Reactivity Parameters and Ground-State Characteristics of Complexes-Are They Justifiable?

Abstract

This article appraises the possibility and justification for searching out correlations between excited-state photoredox reactivity parameters (quenching constant k_q , threshold energy E _th, quantum yield φ) and ground-state parameters (such as ionization energy I, optical electronegativity x, redox potential E ⁰, Taft parameters σ _T and Hammett parameters σ _H ) of complexes, their ligands and central atoms. Based on experimental data this paper deals with the question of whether the existence of such correlations, and in which cases, can be justified.

Key Words:

• photochemistry
• reactivity
• electron transfer
• photoredox reactions