Do nonplanar distortions of porphyrins bring about strongly red-shifted electronic spectra? Controversy, consensus, new developments, and relevance to chelatases

Hege Ryeng; Abhik Ghosh

doi:10.1021/ja0202659

Do nonplanar distortions of porphyrins bring about strongly red-shifted electronic spectra? Controversy, consensus, new developments, and relevance to chelatases

J Am Chem Soc. 2002 Jul 10;124(27):8099-103. doi: 10.1021/ja0202659.

Authors

Hege Ryeng¹, Abhik Ghosh

Affiliation

¹ Department of Chemistry, Faculty of Science, University of Tromsø, N-9037 Tromsø, Norway.

PMID: 12095355
DOI: 10.1021/ja0202659

Abstract

TDDFT calculations confirm a controversial proposal by DiMagno and co-workers that ruffling distortions, by themselves, do not bring about sizable red shifts in the electronic absorption spectra of "simple" nontransition-metal porphyrins. We now report that the same also holds for saddling distortions. The situation is more complex for transition metal porphyrins. For example, ruffling does bring about strong red shifts in the electronic spectra of nickel porphyrins because of a specific metal(d)-porphyrin(pi) orbital interaction.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Metalloporphyrins / chemistry*
Models, Molecular
Molecular Conformation
Nickel / chemistry*
Spectrum Analysis
Thermodynamics

Substances

Metalloporphyrins
Nickel