Photoinduced Intramolecular Tryptophan Oxidation and Excited-State Behavior of [Re(L-AA)(CO)3(r-diimine)] þ (L = Pyridine or Imidazole, AA = Tryptophan, Tyrosine, Phenylalanine)

0360627 - ÚFCH JH 2012 RIV US eng J - Journal Article
Blanco-Rodríguez, A. M. - Towrie, M. - Sýkora, Jan - Záliš, Stanislav - Vlček, Antonín
Photoinduced Intramolecular Tryptophan Oxidation and Excited-State Behavior of [Re(L-AA)(CO)3(r-diimine)] þ (L = Pyridine or Imidazole, AA = Tryptophan, Tyrosine, Phenylalanine).
Inorganic Chemistry. Roč. 50, č. 13 (2011), s. 6122-6134. ISSN 0020-1669. E-ISSN 1520-510X
R&D Projects: GA MŠMT(CZ) LD11082
Institutional research plan: CEZ:AV0Z40400503
Keywords : tryptophan * tyrosine * phenylalanine
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 4.601, year: 2011

ReI carbonyl-diimine complexes [Re(L-AA)(CO)3(N,N)]+ (N,N = bpy, phen) containing an aromatic amino acid (AA), phenylalanine (Phe), tyrosine (Tyr), or tryptophan (Trp), linked to Re by a pyridine-amido or imidazole-amido ligand L have been synthesized and their excited-state properties investigated by nanosecond time-resolved IR (TRIR) and emission spectroscopy. Near-UV optical excitation populates a ReI(CO)3→N,N 3MLCT excited state *[ReII(L-AA)(CO)3(N,N•–)]+. Decay to the ground state (50–300 ns lifetime) is the only excited-state deactivation process observed in the case of Phe and Tyr complexes, whereas the Trp-containing species undergo a Trp(indole)→*ReII electron transfer (ET) producing a charge-separated (CS) state, [ReI(L-Trp•+)(CO)3(N,N•–)]+. The ET occurs with a 8–40 ns lifetime depending on L, N,N, and the solvent.
Permanent Link: http://hdl.handle.net/11104/0006493