Bachmann J (2005)
Publication Status: Published
Publication Type: Journal article, Original article
Publication year: 2005
Publisher: American Chemical Society
Book Volume: 44
Pages Range: 6930-6932
DOI: 10.1021/ic0511017
The lowest-energy optical transition of two-electron-oxidized porphyrinogens [(LM)-M-Delta] is a ligand-based charge transfer. The color of the intermediary, two-electron mixed-valent oxidation state shifts from vermilion (lambda(max) = 480 nm) to yellow (lambda(max) = 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 [(LM)-M-Delta] compounds, the position of M2+ relative to the dianionic dipyrrole unit.
APA:
Bachmann, J. (2005). Structural tuning of ligand-based two-electron intervalence charge transfer. Inorganic Chemistry, 44, 6930-6932. https://doi.org/10.1021/ic0511017
MLA:
Bachmann, Julien. "Structural tuning of ligand-based two-electron intervalence charge transfer." Inorganic Chemistry 44 (2005): 6930-6932.
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