The solid-state E/Z-photoisomerization of 1,2-dibenzoylethene .
The E/Z-photoisomerization of trans-1,2-dibenzoylethene (DBE) in the confinement of its crystal lattice proceeds readily, but not as a single crystal to single crystal process which was claimed previously by others. This model for the Z-->E isomerization at the 11-12 double bond of the retinal moiety in the crystal-like confinement of rhodopsin was investigated in view of the fact that the precise geometric features are crucial for a better understanding of the postulated twist mechanism. Atomic force microscopy (AFM) monitored long-range anisotropic molecular movements if trans-DBE was photoisomerized, but cis-DBE was unreactive even at the extreme sensitivity of AFM. The crystal lattices of both isomers cannot accommodate a rotational mechanism but at best the twist mechanism with the large groups not leaving their planes. The unidirectional solid-state photochemistry derives from the crystal packing of cis-DBE which exhibits severe 3D-interlocking. Thus, trans-DBE molecules are not formed in the cis-lattice, because their moving away would be prohibited. Conversely, photochemically formed cis-DBE molecules escape the foreign trans-DBE lattice easily along its glide planes, as is experimentally observed by AFM. These findings are reminiscent of the escape of 11-trans-retinal from the rhodopsin array in the vision cascade.
Kaupp
G
G
Organic Chemistry I, University of Oldenburg, Germany. kaupp@kaupp.chemie.uni-oldenburg.de
Schmeyers
J
J
D005030:Ethylenes / Q000737:chemistry*; D007536:Isomerism; D018625:Microscopy, Atomic Force / Q000379:methods; D015394:Molecular Structure
C438953:1,2-dibenzoylethene; D005030:Ethylenes