PHOTOINDUCED PROCESSES IN DYADS AND TRIADS - AN OSMIUM(II)-BIS(TERPYRIDINE) PHOTOSENSITIZER COVALENTLY LINKED TO ELECTRON-DONOR AND ACCEPTOR GROUPS

被引:72
作者
COLLIN, JP
GUILLEREZ, S
SAUVAGE, JP
BARIGELLETTI, F
DECOLA, L
FLAMIGNI, L
BALZANI, V
机构
[1] CNR, IST FRAE, I-40126 BOLOGNA, ITALY
[2] UNIV STRASBOURG 1, INST CHIM, CHIM ORGANOMINERALE LAB, F-67070 STRASBOURG, FRANCE
[3] UNIV BOLOGNA, DIPARTIMENTO CHIM G CIAMICIAN, I-40126 BOLOGNA, ITALY
关键词
D O I
10.1021/ic00046a023
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We have synthesized the luminescent Os(ttP)22+ photosensitizer (P) and the supramolecular species P-A, D-P, and D-P-A where the photosensitizer is covalently linked to the electron acceptor MV2+ (A) and/or the electron donors PTZ or DPAA (D); ttp is 4'-(p-tolyl)-2,2':6',2"-terpyridine, MV2+ is methylviologen, PTZ is phenothiazine, and DPAA is di-p-anisylamine. The absorption spectra, emission spectra and lifetimes in the nano- and picosecond time scales (in the 90-298 K temperature range), nanosecond transient absorption spectra and lifetimes (at 155 and 298 K), and the electrochemical behavior of the P, P-A, D-P, and D-P-A species have been investigated in acetonitrile or butyronitrile solutions. The main results can be summarized as follows: (i) the excited photosensitizer *P displays luminescence and decays with tau = 540 and 220 ns at 155 and 298 K respectively; (ii) the behavior of the D-P dyads, whose D+-P- charge-separated state lies at higher energy than the luminescent D-*P level, is essentially the same as that of P; (iii) in the P-A dyad, whose P+-A- charge-separated level lies at lower energy than the *P-A luminescent level, the luminescence intensity of the photosensitizer reduces to 1.9% and exhibits a lifetime of 4 ns at 155 K (260 ps at 298 K); the decay of the charge-separated species occurs with lifetime 27 ns and < 10 ns at 155 and 298 K respectively; (iv) the D-P-A triad with D = PTZ behaves essentially as the P-A dyad; (v) for the D-P-A triad with D = DPPA, the luminescence intensity reduces to approximately 1% at 298 K (tau = 190 ps). No direct evidence is obtained for the presence and survival of the fully charge-separated state D+-P-A-. In a rigid matrix at 77 and 90 K, no quenching of the luminescence can be observed in all the dyads and triads examined.
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页码:4112 / 4117
页数:6
相关论文
共 35 条
[1]   MODELING LONG-RANGE PHOTOSYNTHETIC ELECTRON-TRANSFER IN RIGIDLY BRIDGED PORPHYRIN QUINONE SYSTEMS [J].
ANTOLOVICH, M ;
KEYTE, PJ ;
OLIVER, AM ;
PADDONROW, MN ;
KROON, J ;
VERHOEVEN, JW ;
JONKER, SA ;
WARMAN, JM .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (05) :1933-1941
[2]  
BALZANI V, 1991, SUPRAMOLECULAR PHOTO, pCH5
[3]   PHOTOINDUCED CHARGE SEPARATION IN A PORPHYRIN TETRAVIOLOGEN SUPRAMOLECULAR ARRAY [J].
BATTEAS, JD ;
HARRIMAN, A ;
KANDA, Y ;
MATAGA, N ;
NOWAK, AK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (01) :126-133
[4]   2,2'-4,4''-4',4'''-QUATERPYRIDYL - A BUILDING BLOCK FOR THE PREPARATION OF NOVEL REDOX REAGENTS .2. BIS(2,2'-BIPYRIDINE)RUTHENIUM(II) COMPLEXES [J].
BIERIG, K ;
MORGAN, RJ ;
TYSOE, S ;
GAFNEY, HD ;
STREKAS, TC ;
BAKER, AD .
INORGANIC CHEMISTRY, 1991, 30 (26) :4898-4903
[5]  
BILLON JP, 1962, ANN CHIM FRANCE, V7, P183
[6]   INTRAMOLECULAR LONG-DISTANCE ELECTRON-TRANSFER IN ORGANIC-MOLECULES [J].
CLOSS, GL ;
MILLER, JR .
SCIENCE, 1988, 240 (4851) :440-447
[7]   SYNTHESIS OF FUNCTIONALIZED ASYMMETRICAL BIS(TERPYRIDINE)OSMIUM(II) COMPLEXES UNDER MILD CONDITIONS [J].
COLLIN, JP ;
GUILLEREZ, S ;
SAUVAGE, JP .
INORGANIC CHEMISTRY, 1990, 29 (24) :5009-5010
[8]   RUTHENIUM AND OSMIUM COMPLEXES OF 2,2' - 6',2''-TERPYRIDINE COVALENTLY LINKED TO ELECTRON-ACCEPTOR AND ELECTRON-DONOR GROUPS [J].
COLLIN, JP ;
GUILLEREZ, S ;
SAUVAGE, JP .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (12) :776-778
[9]   PHOTOINDUCED PROCESSES IN DYADS AND TRIADS CONTAINING A RUTHENIUM(II) BIS(TERPYRIDINE) PHOTOSENSITIZER COVALENTLY LINKED TO ELECTRON-DONOR AND ACCEPTOR GROUPS [J].
COLLIN, JP ;
GUILLEREZ, S ;
SAUVAGE, JP ;
BARIGELLETTI, F ;
DECOLA, L ;
FLAMIGNI, L ;
BALZANI, V .
INORGANIC CHEMISTRY, 1991, 30 (22) :4230-4238
[10]  
Connolly J.S., 1988, PHOTOINDUCED ELECT D, P303