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• W2324622304 abstract "We combine femtosecond polarization resolved VIS-pump IR-probe spectroscopy with DFT and TD-DFT calculations to identify and assign absorption bands to electronic transitions for corroles. These macrocycles and their corresponding metal complexes are receiving great attention because of their utility in many fields, while many of their spectroscopic features have not yet been fully described. Analysis of the perturbed free induction decay provides information about the bleaching signal at time zero and allows for determination of overlapping excited state and bleaching signal amplitudes. The S0 → S1 and S0 → S2 transitions in the Q-band of the hexacoordinated Al(tpfc)(py)2 and Br8Al(tpfc)(py)2 absorption spectra are explicitly assigned. Angles between these electronic transition dipole moments (tdms) with a single vibrational transition dipole moment of (53 ± 2)° and (34 ± 2)° when excited at 580 and 620 nm for hexacoordinated Al(tpfc)(py)2 and (51 ± 2)° and (43 ± 2)° when excited at 590 and 640 nm for hexacoordinated Br8Al(tpfc)(py)2 were determined. The relative angles between the two lowest electronic tdms are (90 ± 8)° and (94 ± 3)° for Al(tpfc)(py)2 and Br8Al(tpfc)(py)2, respectively. Angles are determined before time zero by polarization resolved perturbed free induction decay and after time zero by polarization resolved transients. Comparison of corrole’s wave functions with those of porphine show that the reduced symmetry in the corrole molecules results in lifting of Q-band degeneracy and major reorientation of the electronic transition dipole moments within the molecular scaffold. This information is necessary in designing optimal corrole-based electron and energy transfer complexes." @default.
• W2324622304 created "2016-06-24" @default.
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• W2324622304 date "2012-01-17" @default.
• W2324622304 modified "2023-10-03" @default.
• W2324622304 title "Assignment of Aluminum Corroles Absorption Bands to Electronic Transitions by Femtosecond Polarization Resolved VIS-Pump IR-Probe Spectroscopy" @default.
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• W2324622304 doi "https://doi.org/10.1021/jp211970j" @default.
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• W2324622304 hasPublicationYear "2012" @default.
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