Characterization of the unusual metal-free, zinc, chloroindium, and ferrocenylindium 5,10,15,20-tetraferrocenylporphyrin anion-radicals by spectroelectrochemical, DFT, and TDDFT approaches

Victor N. Nemykin, Ping Chen, Pavlo Solntsev, Anatolii A. Purchel, Karl M. Kadish

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Abstract

Anion-radicals of general formula [MTFcP]- (M = 2H, Zn, InCl, and InFc; TFcP2- is a dianion of 5,10,15,20-tetraferrocenylporphyrin) were prepared for the first time in situ by controlled potential reduction of the respective neutral MTFcP complexes in a thin layer spectroelectrochemical cell. UV-vis spectroscopy reveals the formation of a broad NIR band between 827-890 nm and another broad band in the Soret region between 458 and 527 nm. A similar NIR band has previously been assigned to 5,10,15,20-tetra(aryl)porphyrin radical-anions. Additional information on the electronic structure and nature of the vertical excitation energies in the [H2TFcP]- system were obtained by density functional theory (DFT) and time-dependent DFT (TDDFT) methods. DFT calculations predict that the SOMO in the [H 2TFcP]- anion-radical is predominantly localized over the porphyrin core. TDDFT calculations suggest numerous MLCT transitions in addition to the expected π-π* excitations, which play a key role in the formation of unusual UV-vis spectra in the [MTFcP]- anion-radicals.

Original languageEnglish (US)
Pages (from-to)793-801
Number of pages9
JournalJournal of Porphyrins and Phthalocyanines
Volume16
Issue number7-8
DOIs
StatePublished - 2012

Bibliographical note

Funding Information:
Generous support from the NSF CHE-1110455, the Minnesota Supercomputing Institute to VN, and the from the Robert A. Welch Foundation (K.M.K, Grant E-680) are greatly appreciated.

Keywords

  • density functional theory
  • electrochemistry
  • ferrocene-containing porphyrins
  • porphyrin anion-radicals
  • spectroelectrochemistry
  • time-dependent density functional theory

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