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Bachmann J, Nocera DG. Structural tuning of ligand-based two-electron intervalence charge transfer. Inorg Chem. 2005;44(20):6930-2doi: 10.1021/ic0511017.
Bachmann, J., & Nocera, D. G. (2005). Structural tuning of ligand-based two-electron intervalence charge transfer. Inorganic chemistry, 44(20), 6930-2. https://doi.org/10.1021/ic0511017
Bachmann, Julien, and Nocera, Daniel G. "Structural tuning of ligand-based two-electron intervalence charge transfer." Inorganic chemistry vol. 44,20 (2005): 6930-2. doi: https://doi.org/10.1021/ic0511017
Bachmann J, Nocera DG. Structural tuning of ligand-based two-electron intervalence charge transfer. Inorg Chem. 2005 Oct 03;44(20):6930-2. doi: 10.1021/ic0511017. PMID: 16180852.
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Inorg Chem. 2005 Oct 03;44(20):6930-2. doi: 10.1021/ic0511017.

Structural tuning of ligand-based two-electron intervalence charge transfer.

Inorganic chemistry

Julien Bachmann, Daniel G Nocera

Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139-4207, USA.

PMID: 16180852 DOI: 10.1021/ic0511017

Abstract

The lowest-energy optical transition of two-electron-oxidized porphyrinogens [L(Delta)M] is a ligand-based charge transfer. The color of the intermediary, two-electron mixed-valent oxidation state shifts from vermilion (lambdamax = 480 nm) to yellow (lambdamax = 270 nm) upon increasing the ionic radius of the central metal dication from Mg2+ to Zn2+ and Ca2+. Structural, spectroscopic, and computational studies establish that the relative energies of the highest occupied and lowest unoccupied orbitals, between which the intervalence charge-transfer optical transition occurs, are modulated by the molecular dipole moment, which in turn depends on the only structural variable among the [L(Delta)M] compounds, the position of M2+ relative to the dianionic dipyrrole unit.

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