期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 23, 期 26, 页码 6357-6369出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201700043
关键词
donor-acceptor systems; electron transfer; Marcus theory; photochemistry; porphyrinoids
资金
- ERC Advanced Grant [246637]
- Swiss National Science Foundation [SNF 200020_159802]
- Solar Technologies Go Hybrid network from the Bavarian state
- Universitat Bayern e.V.
- European Research Council (ERC) [246637] Funding Source: European Research Council (ERC)
We report on a series of electron donor-acceptor conjugates incorporating a Zn-II-porphyrin-based electron donor and a variety of non-conjugated rigid linkers connecting to push-pull chromophores as electron acceptors. The electron acceptors comprize multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from -1.67 to -0.23V vs. Fc(+)/Fc in CH2Cl2, which are accessible through a final-step cycloaddition-retroelectrocyclization (CA-RE) reaction. Characterization of the conjugates includes electrochemistry, spectroelectrochemistry, DFT calculations, and photophysical measurements in a range of solvents. The collected data allows for the construction of multiple Marcus curves that consider electron-acceptor strength, linker length, and solvent, with data points extending well into the inverted region. The enhancement of electron-vibration couplings, resulting from the rigid spacers and, in particular, multicyano-groups in the conformationally highly fixed push-pull acceptor chromophores affects the charge-recombination kinetics in the inverted region drastically.
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