| Autor: |
Nevonen DE; Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States., Wagner JC; Department of Chemistry, University of Akron, Akron, Ohio 44325-3601, United States., Brückner C; Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, United States., Ziegler CJ; Department of Chemistry, University of Akron, Akron, Ohio 44325-3601, United States., Nemykin VN; Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States. |
| Abstrakt: |
We report a systematic investigation of a series of Ag(II) and Ag(III) complexes of porphyrins and their analogues using UV-vis magnetic circular dichroism (MCD) spectroscopies and theoretical calculations. Ag(II) and Ag(III) octaethyl- and tetraarylporphyrins show the usual sign sequence in the Q-band region (i.e., negative to positive intensities with increasing energy) of their MCD spectra, indicative of the ΔHOMO > ΔLUMO relationship (ΔHOMO is the energy difference between Michl's a and s orbitals, and ΔLUMO is the energy difference between Michl's -a and - s pair of MOs). In contrast, Ag(II) complexes of β,β'-pyrrole-modified porphyrins (with an effective chlorin-type π-system) and Ag(III) corroles have sign reverse features in the MCD spectra of their Q-band region (ΔHOMO < ΔLUMO relationships). The Ag(III) complex of N-confused porphyrin shows the ΔHOMO > ΔLUMO relationship in the neutral state and the ΔHOMO < ΔLUMO relationship in the protonated form. |
