A perspective on the redox properties of tetrapyrrole macrocycles

Diers, James R.; Kirmaier, Christine; Taniguchi, Masahiko; Lindsey, Jonathan S.; Bocian, David F.; Holten, Dewey

doi:10.1039/d1cp01943k

A perspective on the redox properties of tetrapyrrole macrocycles

Journal Article · Tue Sep 07 00:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp01943k· OSTI ID:1830805

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Univ. of California, Riverside, CA (United States); Washington University
Washington Univ., St. Louis, MO (United States)
North Carolina State Univ., Raleigh, NC (United States)
Univ. of California, Riverside, CA (United States)

Tetrapyrrole macrocycles serve a multitude of roles in biological systems, including oxygen transport by heme and light harvesting and charge separation by chlorophylls and bacteriochlorophylls. Synthetic tetrapyrroles are utilized in diverse applications ranging from solar-energy conversion to photomedicine. Nevertheless, students beginning tetrapyrrole research, as well as established practitioners, are often puzzled when comparing properties of related tetrapyrroles. Questions arise as to why optical spectra of two tetrapyrroles often shift in wavelength/energy in a direction opposite to that predicted by common chemical intuition based on the size of a π-electron system. Gouterman's four-orbital model provides a framework for understanding these optical properties. Similarly, it can be puzzling as to why the oxidation potentials differ significantly when comparing two related tetrapyrroles, yet the reduction potentials change very little or shift in the opposite direction. In order to understand these redox properties, it must be recognized that structural/electronic alterations affect the four frontier molecular orbitals (HOMO, LUMO, HOMO-1 and LUMO+1) unequally and in many cases the LUMO+1, and not the LUMO, may track the HOMO in energy. This perspective presents a fundamental framework concerning tetrapyrrole electronic properties that should provide a foundation for rational molecular design in tetrapyrrole science.

View Accepted Manuscript (DOE)

Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-05ER15661

OSTI ID:: 1830805

Alternate ID(s):: OSTI ID: 1818997

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 35 Vol. 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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A perspective on the redox properties of tetrapyrrole macrocycles

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