Vibrational Circular Dichroism Detects Symmetry Breaking due to Conformational Mobility in C2-Symmetry Chiral Molecules and Provides Further Insight into Inter-Chromophoric Interactions

Bicyclo[3.3.1]nonane-2,6-dione (1) and bicyclo[3.3.1]nona-3,7-diene-2,6-dione (2) have been examined by vibrational circular dichroism (VCD), which, as for most C2-symmetric systems, exhibits strong VCD signals. In the case of 2, VCD signals are stronger and sharper with several bisignate doublets; for 1, signals are less intense and broader. The VCD and IR spectra are excellently predicted by DFT calculations: only one conformer is present for 2, while for 1, three main conformers, related through concerted skeleton torsional motions are present (two of them being interchanged by C2-rotation). The VCD spectrum shows specific features for the different conformers, such that correct population factors are crucial for reproducing experimental data. Also, the TD-DFT prediction of ECD (electronic circular dichroism) spectra is good. By comparing the spectroscopic signature of the two molecules (both VCD and ECD) and by careful analysis of the theoretical results, the role of the C=C double bond in compound (2) is evidenced. The double bond contributes toward enhancing the CD response both electronically and vibrationally

Insights into the Structures of Bilirubin and Biliverdin from Vibrational and Electronic Circular Dichroism: History and Perspectives

: In this work we review research activities on a few of the most relevant structural aspects of bilirubin (BR) and biliverdin (BV). Special attention is paid to the exocyclic C=C bonds being in mostly Z rather than E configurations, and to the overall conformation being essentially different for BR and BV due to the presence or absence of the double C=C bond at C-10. In both cases, racemic mixtures of each compound of either M or P configuration are present in achiral solutions; however, imbalance between the two configurations may be easily achieved. In particular, results based on chiroptical spectroscopies, both electronic and vibrational circular dichroism (ECD and VCD) methods, are presented for chirally derivatized BR and BV molecules. Finally, we review deracemization experiments monitored with ECD data from our lab for BR in the presence of serum albumin and anesthetic compounds