Do Nonplanar Distortions of Porphyrins Bring about Strongly Red-Shifted Electronic Spectra? Controversy, Consensus, New Developments, and Relevance to Chelatases
- 12 June 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (27) , 8099-8103
- https://doi.org/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(π) orbital interaction.Keywords
This publication has 12 references indexed in Scilit:
- Nonplanar porphyrins and their biological relevance: Ground and excited state dynamicsPublished by Springer Nature ,2006
- Chemistry with ADFJournal of Computational Chemistry, 2001
- On the Negligible Impact of Ruffling on the Electronic Spectra of Porphine, Tetramethylporphyrin, and PerfluoroalkylporphyrinsJournal of the American Chemical Society, 2001
- Do Nonplanar Porphyrins Have Red-Shifted Electronic Spectra? A DFT/SCI Study and Reinvestigation of a Recent ProposalJournal of the American Chemical Society, 2000
- A First-Principles Quantum Chemical Analysis of the Factors Controlling Ruffling Deformations of Porphyrins: Insights from the Molecular Structures and Potential Energy Surfaces of Silicon, Phosphorus, Germanium, and Arsenic Porphyrins and of a Peroxidase Compound I ModelJournal of the American Chemical Society, 1999
- Theoretical Studies of Low-Spin Six-Coordinate Iron(III) Porphyrins Relevant to Cytochromes b: Variable Electronic Configurations, Ligand Noninnocence, and Macrocycle RufflingThe Journal of Physical Chemistry B, 1999
- Nonplanar porphyrins and their significance in proteinsChemical Society Reviews, 1998
- Resonance Raman Spectra of Ferrochelatase Reveal Porphyrin Distortion upon Metal BindingJournal of the American Chemical Society, 1997
- Electronic Consequences of Nonplanar Core Conformations in Electron-Deficient Porphyrins: The Structure and Spectroscopic Properties of [5,10,15,20-Tetrakis(heptafluoropropyl)porphinato]cobalt(II)Journal of the American Chemical Society, 1995
- Antibody-Catalyzed Porphyrin MetallationScience, 1990