期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 52, 页码 16844-16867出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201200956
关键词
density functional calculations; fluorescence; MCD spectroscopy; porphyrinoids; ring expansion
资金
- Major State Basic Research Development Program of China [2011CB808704]
- National Natural Science Foundation of China [20971066, 21021062]
- Ministry of Education, Culture, Sports, Science, and Technology, Japan (MEXT) [20108007, 23350095]
- Alexander-von-Humboldt Foundation
- European Commission
- Adolf-Martens Fonds
- Grants-in-Aid for Scientific Research [23350095, 20108007] Funding Source: KAKEN
The synthesis of a series of novel core-modified and fused-ring-expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem-crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine-tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso-phenyl rings, is also examined.
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