Treatment of meso-chlorosubporphyrin with controlled equivalents of Na2S·9H2O in DMF led to the formation of either meso-to-meso sulfide (S)-bridged dimer 4 or disulfide (SS)-bridged subporphyrin dimer 6. S-bridged dimer 4 displayed a split Soret-like band and a large Stokes shift and became a fully delocalized one-quantum system in the S1 state, as indicated by femtosecond transient absorption anisotropy measurements and theoretical calculations. Contrastingly, SS-bridged dimer 6 showed a broad but nonsplit Soret-like band, no fluorescence, and very fast S1 decay with a lifetime of 4 ps, which indicated the presence of a rapid decay channel.
Bibliographical noteFunding Information:
The work at Kyoto was supported by Grants-in-Aid for Scientific Research (KAKENHI) from the Japan Society for the Promotion of Science (JSPS) (Grant Numbers 25220802, 25620031, and 20705446). G. C. thanks the JSPS for a fellowship. The work at Yonsei was supported by the Ministry of Education, Science, and Technology (MEST) of Korea through the Global Research Laboratory (GRL) Program (2013-8-1472). The quantum calculations were performed by using the supercomputing resources of the Korea Institute of Science and Technology Information (KISTI).
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry