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Triplet excitation energy transfer in porphyrin-based donor-bridge-acceptor systems with conjugated bridges of varying length:: An experimental and DFT study
被引:68
作者:
Eng, MP
[1
]
Ljungdahl, T
[1
]
Mårtensson, J
[1
]
Albinsson, B
[1
]
机构:
[1] Chalmers Univ Technol, Dept Chem & Biol Engn, SE-41296 Gothenburg, Sweden
关键词:
D O I:
10.1021/jp056536u
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 series of donor-bridge-acceptor (D-B-A) systems with varying donor-acceptor distances have been studied with respect to their triplet energy transfer properties. The donor and acceptor moieties, zinc(II), and free-base porphyrin, respectively, were separated by 2-5 oligo-p-phenyleneethynylene units (OPE) giving rise to edge-to-edge separations ranging between 12.7 and 33.4 angstrom. The study was performed in 2-MTHF at 150 K and it was established that triplet excitation energy transfer occurs with high efficiency in all of the studied D-B-A systems. The distance dependence was exponential with an attenuation factor, beta, equal to 0.45 +/- 0.015 angstrom(-1). The experimental study was also supported by quantum mechanical DFT and TD-DFT calculations on a series of closely related model systems. A thorough analysis of the OPE-bridge conformational dynamics led to an equation that quantitatively models the distance dependence of the electronic coupling found in the experimental study.
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页码:6483 / 6491
页数:9
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