期刊
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
卷 16, 期 7-8, 页码 793-801出版社
WORLD SCI PUBL CO INC
DOI: 10.1142/S1088424612500745
关键词
ferrocene-containing porphyrins; porphyrin anion-radicals; electrochemistry; spectroelectrochemistry; density functional theory; time-dependent density functional theory
资金
- NSF [CHE-1110455]
- Minnesota Supercomputing Institute
- Robert A. Welch Foundation [E-680]
- Direct For Mathematical & Physical Scien [1110455] Funding Source: National Science Foundation
- Division Of Chemistry [1110455] Funding Source: National Science Foundation
Anion-radicals of general formula [MTFcP](-) (M = 2H, Zn, InCl, and InFc; TFcP(2-) 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 [H(2)TFcP](-) system were obtained by density functional theory (DFT) and time-dependent DFT (TDDFT) methods. DFT calculations predict that the SOMO in the [H(2)TFcP](-) anion-radical is predominantly localized over the porphyrin core. TDDFT calculations suggest numerous MLCT transitions in addition to the expected pi-pi* excitations, which play a key role in the formation of unusual UV-vis spectra in the [MTFcP](-) anion-radicals.
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