Enantioselective magnetochiral photochemistry
Many chemical and physical systems can occur in two forms distinguished solely by being mirror images of each other. This phenomenon, known as chirality, is important in biochemistry, where reactions involving chiral molecules often require the participation of one specific enantiomer (mirror image) of the two possible ones. In fact, terrestrial life utilizes only the L enantiomers of amino acids, a pattern that is known as the 'homochirality of life' and which has stimulated long-standing efforts to understand its origin. Reactions can proceed enantioselectively if chiral reactants or catalysts are involved, or if some external chiral influence is present. But because chiral reactants and catalysts themselves require an enantioselective production process, efforts to understand the homochirality of life have focused on external chiral influences. One such external influence is circularly polarized light, which can influence the chirality of photochemical reaction products. Because natural optical activity, which occurs exclusively in media lacking mirror symmetry, and magnetic optical activity, which can occur in all media and is induced by longitudinal magnetic fields, both cause polarization rotation of light, the potential for magnetically induced enantioselectivity in chemical reactions has been investigated, but no convincing demonstrations of such an effect have been found. Here we show experimentally that magnetochiral anisotropy--an effect linking chirality and magnetism--can give rise to an enantiomeric excess in a photochemical reaction driven by unpolarized light in a parallel magnetic field, which suggests that this effect may have played a role in the origin of the homochirality of life.
Rikken
G L
GL
Grenoble High Magnetic Field Laboratory, Max Planck Institut fur Festkorperforschung/CNRS, France. rikken@polycnrs-gre.fr
Raupach
E
E
D016880:Anisotropy; D002840:Chromates / Q000737:chemistry* / Q000528:radiation effects; D019418:Evolution, Chemical; D018559:Exobiology; D008027:Light; D008280:Magnetics; D000069497:Origin of Life; D010070:Oxalates / Q000737:chemistry* / Q000528:radiation effects; D010777:Photochemistry; D011188:Potassium / Q000737:chemistry; D013237:Stereoisomerism
D002840:Chromates; D010070:Oxalates; C054506:tris(oxalato)chromate(III); D011188:Potassium