Dg. Mccafferty et al., PHOTOCHEMICAL ENERGY-CONVERSION IN A HELICAL OLIGOPROLINE ASSEMBLY, Proceedings of the National Academy of Sciences of the United Statesof America, 93(16), 1996, pp. 8200-8204
A general method is described for constructing a helical oligoproline
assembly having a spatially ordered array of functional sites protrudi
ng from a proline-II helix, Three different redox-active carboxylic ac
ids were coupled to the side chain of cis-4-amino-L-proline. These red
ox modules were incorporated through solid-phase peptide synthesis int
o a 13-residue helical oligoproline assembly bearing in linear array a
phenothiazine electron donor, a tris(bipyridine)ruthenium(II) chromop
hore, and an anthraquinone electron acceptor, Upon transient 460-nm ir
radiation in acetonitrile, this peptide triad formed with 53% efficien
cy an excited state containing a phenothiazine radical cation and an a
nthraquinone radical anion, This light-induced redox-separated state h
ad a lifetime of 175 ns and stored 1.65 eV of energy.