Distance dependence of intrahelix Ru(II)* to Os(II) polypyridyl excited-state energy transfer in oligoproline assemblies.

Energy transfer between the metal-to-ligand charge transfer (MLCT) excited states of [Pra [M(II)(bpy)2(4-Me-4'(-N(H)CO)bpy)](PF6)2 units ([Pra(M(II)bpy2(mbpy)](2+): M(II) = Ru(II) or Os(II), bpy = 2,2'-bipyridine, mbpy = 4'-methyl-2,2'-bipyridine-4-carboxamido, Pra = 4-M(II)-L-proline) linked covalently to oligoproline assemblies in room temperature acetonitrile occurs on the picosecond-nanosecond time scale and has been time-resolved by transient emission measurements. Three derivatized oligoprolines, [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-2, Pro = L-proline and Glu = glutamic acid); [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-3); and CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)Pro6-Glu2-NH2](6+) (ORR-5), were prepared by using solid-phase peptide synthesis. Given the helical nature of the resulting assemblies and the nature of the synthesis, composition, length, and loading pattern are precisely controlled in the assemblies.

Photoelectrochemistry on Ru(II)-2,2'-bipyridine-phosphonate-derivatized TiO2 with the I3-/I- and quinone/hydroquinone relays. Design of photoelectrochemical synthesis cells.

Photocurrent measurements have been made on nanocrystalline TiO2 surfaces derivatized by adsorption of a catalyst precursor, [Ru(tpy)(bpy(PO3H2)2)(OH2)]2+, or chromophore, [Ru(bpy)2 (bpy(PO3H2)2)]2+ (tpy is 2,2':6',2' '-terpyridine, bpy is 2,2'-bipyridine, and bpy(PO3H2)2 is 2,2'-bipyridyl-4,4'-diphosphonic acid), and on surfaces containing both complexes. This is an extension of earlier work on an adsorbed assembly containing both catalyst and chromophore. The experiments were carried out with the I3-/I- or quinone/hydroquinone (Q/H2Q) relays in propylene carbonate, propylene carbonate-water mixtures, and acetonitrile-water mixtures.

Evidence for through-space electron transfer in the distance dependence of normal and inverted electron transfer in oligoproline arrays.

Four new helical oligoproline assemblies containing 16, 17, 18, and 19 proline residues and ordered arrays of a Ru(II)-bipyridyl chromophore and a phenothiazine electron-transfer donor have been synthesized in a modular fashion by solid-phase peptide synthesis. These arrays are illustrated and abbreviated as CH(3)CO-Pro(6)-Pra(PTZ)-Pro(n)()-Pra(Ru(II)b(2)m)(2+)-Pro(6)-NH(2), where PTZ is 3-(10H-phenothiazine-10)propanoyl and (Ru(II)b'(2)m)(2+) is bis(4,4'-diethylamide-2,2'-bipyridine)(4-methyl,4'-carboxylate,2,2'-bipyridine)ruthenium(II) dication with n = 2 (2), 3 (3), 4 (4), and 5 (5). They contain PTZ as an electron-transfer donor and (Ru(II)b'(2)m)(2+) as a metal-to-ligand charge transfer (MLCT) light absorber and are separated by proline-to-proline through-space distances ranging from 0 (n = 2) to 12.