Intramolecular energy transfer in S1- and S2-states of porphyrin trimers

被引:43
作者
Nakano, A
Yasuda, Y
Yamazaki, T
Akimoto, S
Yamazaki, I [1 ]
Miyasaka, H
Itaya, A
Murakami, M
Osuka, A
机构
[1] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan
[2] Hokkaido Univ, Grad Sch Engn, Dept Chem Proc Engn, Sapporo, Hokkaido 0608628, Japan
[3] Kyoto Inst Technol, Dept Polymer Sci & Engn, Kyoto 6068585, Japan
关键词
D O I
10.1021/jp010596s
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A set of four porphyrin trimers (1-4) consisting of an energy-accepting 5,1 5-diphenylethynyl-substituted Zn(II)-porphyrin core flanked by two energy-donating peripheral Zn(IT)-porphyrins have been prepared as a new efficient energy-transfer functional unit. The peripheral porphyrin donor is either a TPP-tppe Zn(II)porphyrin for 1 and 2 or a OEP-type Zn(II)-porphyrin for 3 and 4 and the diphenylethynyl substitution axis of the core porphyrin is aligned either orthogonal in 1 and 3 or parallel in 2 and 4 with respect to the long axis of the trimeric arrays. Femtosecond transient absorption spectroscopy and femtosecond up-conversion fluorescence measurement have revealed the very efficient S-1-S-1 energy-transfer reactions in these porphyrin trimers. The S-1-S-1 energy transfer is faster in the parallel trimers 2 and 4 than in the orthogonal trimers 1 and 3, reflecting larger electronic coupling in the former pair. The peripheral porphyrin S-2-state lifetime is considerably shortened in 1-4, which has been ascribed to S-2-S-2 energy transfer. Probably the strong Soret-transitions of both the donor and acceptor lead to large Coulombic interactions, thereby rendering S2-S2 energy transfer effective enough to compete with rapid internal conversion to S-1-state. These results encourage a new strategy for construction of porphyrin-based supramolecular artificial photosynthetic antenna.
引用
收藏
页码:4822 / 4833
页数:12
相关论文
共 118 条
[1]   Excitation relaxation of zinc and free-base porphyrin probed by femtosecond fluorescence spectroscopy [J].
Akimoto, S ;
Yamazaki, T ;
Yamazaki, I ;
Osuka, A .
CHEMICAL PHYSICS LETTERS, 1999, 309 (3-4) :177-182
[2]   Excitation relaxation of carotenoids within the S2 state probed by the femtosecond fluorescence up-conversion method [J].
Akimoto, S ;
Yamazaki, I ;
Takaichi, S ;
Mimuro, M .
CHEMICAL PHYSICS LETTERS, 1999, 313 (1-2) :63-68
[3]   Building molecular wires from the colours of life: conjugated porphyrin oligomers [J].
Anderson, HL .
CHEMICAL COMMUNICATIONS, 1999, (23) :2323-2330
[4]   CONJUGATED PORPHYRIN LADDERS [J].
ANDERSON, HL .
INORGANIC CHEMISTRY, 1994, 33 (05) :972-981
[5]   Photoinduced electron transfer reactions in a porphyrin-viologen complex:: Observation of S2 to S1 relaxation and electron transfer from the S2 state [J].
Andersson, M ;
Davidsson, J ;
Hammarström, L ;
Korppi-Tommola, J ;
Peltola, T .
JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (16) :3258-3262
[6]  
Aratani N, 2000, ANGEW CHEM INT EDIT, V39, P1458, DOI 10.1002/(SICI)1521-3773(20000417)39:8<1458::AID-ANIE1458>3.0.CO
[7]  
2-E
[8]   SOME REACTIONS OF MESO-FORMYLOCTAETHYLPORPHYRIN [J].
ARNOLD, DP ;
JOHNSON, AW ;
MAHENDRAN, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1978, (04) :366-370
[9]   PORPHYRIN DIMERS LINKED BY CONJUGATED BUTADIYNES [J].
ARNOLD, DP ;
NITSCHINSK, LJ .
TETRAHEDRON, 1992, 48 (40) :8781-8792
[10]   ELUCIDATION OF FACTORS AFFECTING THE ELECTRONIC-STRUCTURES OF MAGNESIUM(II) AND ZINC(II) TETRAARYLPORPHYRIN RADICAL CATIONS [J].
BARZILAY, CM ;
SIBILIA, SA ;
SPIRO, TG ;
GROSS, Z .
CHEMISTRY-A EUROPEAN JOURNAL, 1995, 1 (04) :222-231