TY - JOUR
T1 - Photoinduced Electron Transfer in Supramolecular Assemblies Composed of Dialkoxybenzene-Tethered Ruthenium(II) Trisbipyridine and Bipyridinium Salts
AU - Seiler, M.
AU - Dürr, H.
AU - Willner, I.
AU - Joselevich, E.
AU - Doron, A.
AU - Stoddart, J. F.
PY - 1994/4/1
Y1 - 1994/4/1
N2 - Ruthenium(II) tris{4, 4ʹ-bis[(methyleneoxy)tris(ethyleneoxy)(4-methoxybenzene)]-2, 2ʹ-bipyridine} (1), forms supramolecular complexes with N, N'-dimethyl-4, 4ʹ-bipyridinium, MV2+ (2), and with cyclo [bis(N, N'-p-xylylene-4, 4ʹ-bipyridinium)], BXV4+ (3). The association constants of the complexes generated between the dialkoxybenzene-tethered units of 1 and the electron acceptors 2 and 3 correspond to Ka = 28 ± 1 M-1 for MV2+ and Ka = 1200 ± 100 M-1 for BXV4+. Time-resolved laser flash photolysis and steady-state emission studies show that electron transfer from excited 1 proceeds by an intramolecular pathway to the electron acceptors organized in the supramolecular assemblies, kiq = 1.7 X 108 s-1 for MV2+ and kiq = 2.9 X 108 s-1 for BXV4+, and by a diffusional route from free-uncomplexed 1, kdq = 1.9 X 108 M-1 s-1 for MV2+ and kdq = 3.4 X 108 M-1 s-1 for BXV4+. Formation of the supramolecular assemblies between 1 and 2 or 3 is supported by the intramolecular electron-transfer quenching of 1 and by the fact that the assemblies dissociate upon addition of β-cyclodextrin.
AB - Ruthenium(II) tris{4, 4ʹ-bis[(methyleneoxy)tris(ethyleneoxy)(4-methoxybenzene)]-2, 2ʹ-bipyridine} (1), forms supramolecular complexes with N, N'-dimethyl-4, 4ʹ-bipyridinium, MV2+ (2), and with cyclo [bis(N, N'-p-xylylene-4, 4ʹ-bipyridinium)], BXV4+ (3). The association constants of the complexes generated between the dialkoxybenzene-tethered units of 1 and the electron acceptors 2 and 3 correspond to Ka = 28 ± 1 M-1 for MV2+ and Ka = 1200 ± 100 M-1 for BXV4+. Time-resolved laser flash photolysis and steady-state emission studies show that electron transfer from excited 1 proceeds by an intramolecular pathway to the electron acceptors organized in the supramolecular assemblies, kiq = 1.7 X 108 s-1 for MV2+ and kiq = 2.9 X 108 s-1 for BXV4+, and by a diffusional route from free-uncomplexed 1, kdq = 1.9 X 108 M-1 s-1 for MV2+ and kdq = 3.4 X 108 M-1 s-1 for BXV4+. Formation of the supramolecular assemblies between 1 and 2 or 3 is supported by the intramolecular electron-transfer quenching of 1 and by the fact that the assemblies dissociate upon addition of β-cyclodextrin.
UR - http://www.scopus.com/inward/record.url?scp=0001233699&partnerID=8YFLogxK
U2 - 10.1021/ja00087a026
DO - 10.1021/ja00087a026
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AN - SCOPUS:0001233699
SN - 0002-7863
VL - 116
SP - 3399
EP - 3404
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 8
ER -