Predicting reduction potentials of 1,3,6‐triphenyl fulvenes using molecular electrostatic potential analysis of substituent effects

Abstract

The influence of mono- and multiple substituent effect on the reduction potential (E ) of 1,3,6-triphenyl fulvenes is investigated using B3LYP-SMD/6-311+G(d,p) level density functional theory. The molecular electrostatic potential (MESP) minimum at the fulvene π-system (V ) and the change in MESP at any of the fulvene carbon atoms (ΔV ) for both neutral and reduced forms are used as excellent measures of substituent effect from the para and meta positions of the 1,3 and 6-phenyl moieties. Substitution at 6-phenyl para position has led to significant change in E than any other positions. By applying the additivity rule of substituent effects, an equation in ΔV is derived to predict E for multiply substituted fulvenes. Further, E is predicted for a set of 2000 hexa-substituted fulvene derivatives where the substituents and their positions in the system are chosen in a random way. The calculated E agreed very well with the experimental E reported by Godman et al. Predicting E solely by substituent effect offers a simple and powerful way to select suitable combinations of substituents on fulvene system for light harvesting applications. © 2018 Wiley Periodicals, Inc.

Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity

“…176 Extension of such studies to organic systems showed that the influence of mono-and multiple-substituent effects on the reduction potential (E 0 ) of 1, 3, 6-triphenyl fulvenes can be predicted by MESP V min at the fulvene π-system or by MESP at any of the fulvene carbon atoms (V C ). 177 This study also showed that significant change in E 0 occurs when the substituent at para-position of 6-phenyl unit is changed, compared any other positions. Recently, MESP features have been used to study the ground state as well as the absorption-emission properties of a series of 5-phenyl tris(8-hydroxyquinolinato) M(III) complexes (M = Al, Ga, In).…”

“…The MESP analysis at the chromium nucleus ( V Cr ) was very effective for making predictions on the redox properties of the Fischer carbene complexes (FCCs) of chromium 176 . Extension of such studies to organic systems showed that the influence of mono‐ and multiple‐substituent effects on the reduction potential ( E 0 ) of 1, 3, 6‐triphenyl fulvenes can be predicted by MESP V min at the fulvene π ‐system or by MESP at any of the fulvene carbon atoms ( V C ) 177 . This study also showed that significant change in E 0 occurs when the substituent at para ‐position of 6‐phenyl unit is changed, compared any other positions.…”

Absorption and emission properties of 5‐phenyl tris(8‐hydroxyquinolinato) M(III) complexes (M = Al, Ga, In) and correlations with molecular electrostatic potential

“…The works of Suresh et al have given significant momentum to MESP applications and some of the several applications include comprehending substituent effect, lone pairs, resonance effect, inductive effect, non‐covalent bonding, and so forth. Recently, reduction potentials of cobalt complexes, fulvenes, and Fischer carbene complexes of chromium have been predicted with the use of MESP parameters. Recently, Anjali and Suresh interpreted the activation barriers of a large set of palladium (0) catalysts using the critical features of MESP distribution .…”