A spectroscopic analysis of vitamin B12 derivatives.

1. Several vitamin B12 derivatives including descobalt B12 show unusual inversion of their CD signs upon rapid cooling to liquid N2 temperature, although the room temperature CD signs are conserved by a slower cooling to the same temperature. As a possible explanation for this puzzling observation, a micro-environmental birefringence around the chromophore imbedded in an organic glass is proposed. 2. Absorption, fluorescence, phosphorescence, and polarization spectra of descobalt B12 can be correlated with those of porphyrin free bases, as these two molecular systems share many similarites in their electronic structure. 3. Molecular orbital calculations of polarization directions further support the analoby between the spectroscopic characteristics of corrins and porphyrins, and are generally in good agreement with the fluorescence polarization data.