Photoisomerization of 1,2-diphenylcyclopropane sensitized by polypeptides containing naphthalene groups in their side chain

Poly(γ-1-naphthylmethyl L - and DL -glutamate) (PNLG and PNDLG) and copolypeptides of γ-1-naphthylmethyl L -glutamate and γ-benzyl-L -glutamate were used as sensitizers for isomerization of trans-1,2-diphenylcyclopropane. Quantum yields relative to that of 1-methylnaphthalene were measured in dichloroethane (DCE) and dichloroacetic acid (DCA). The relative quantum yield in DCE was smaller than unity for PNLG, but greater than unity for PNDLG and copolypeptides. The result is discussed in terms of increased effective collisional radius and energy trapping by excimer formation. The relative quantum yields in DCA were close to unity except for the copolypeptides of higher γ-benzyl L -glutamate content. This suggests that the naphthalene groups act in the same manner as their monomeric counterparts in the random conformation and that the greater proportion of γ-benzyl L -glutamate in the copolypeptides lowers the quantum efficiency because trans-1,2-diphenylcyclopropane must penetrate through the polymeric medium in order to encounter the excited naphthalene.