Yang, Y; Jones, D; von Haimberger, T; Linke, M; Wagnert, L; Berg, A; Levanon, H; Zacarias, A; Mahammed, A; Gross, Z; Heyne, K

JOURNAL OF PHYSICAL CHEMISTRY A 2012, 116(3), p. 1023-1029;

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 field, 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 Br(8)Al(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 degrees) and (34 ± 2 degrees) when excited at 580 and 620 nm for hexacoordinated Al(tpfc)(py)₂ and (51 ± 2 degrees) and (43 ± 2 degrees) when excited at 590 and 640 nm for hexacoordinated Br(8)Al(tpfc)(py)₂ were determined. The relative angles between the two lowest electronic tdms are (90 ± 8 degrees) and (94 ± 3 degrees) for Al(tpfc)(py)₂ and Br(8)Al(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.

DOI 10.1021/jp211970j