期刊
CHEMPHYSCHEM
卷 13, 期 14, 页码 3370-3382出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201200350
关键词
density functional calculations; donor-acceptor systems; photophysics; porphyrinoids; redox chemistry
资金
- Swiss National Science Foundation [200020-130266/1]
- EU-project [FUNMOLS FP7-212942-1]
- Australian Research Council [FT110100152, DP1093337]
- Global COE (center of excellence) program Global Education and Research Center for Bio-Environmental Chemistry of Osaka University from Ministry of Education, Culture, Sports, Science and Technology, Japan
- KOSEF/MEST through WCU project from Korea [R31-2008-000-10010-0]
- Grants-in-Aid for Scientific Research [23655041, 21102004, 22350018, 20110006, 20108010] Funding Source: KAKEN
- National Research Foundation of Korea [R31-2012-000-10010-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
- Australian Research Council [DP1093337] Funding Source: Australian Research Council
A tetrathiafulvalene (TTF) donor is annulated to porphyrins (P) via quinoxaline linkers to form novel symmetric PTTFP triads 1?ac and asymmetric PTTF dyads 2?a,b in good yields. These planar and extended p-conjugated molecules absorb light over a wide region of the UV/Vis spectrum as a result of additional charge-transfer excitations within the donoracceptor assemblies. Quantum-chemical calculations elucidate the nature of the electronically excited states. The compounds are electrochemically amphoteric and primarily exhibit low oxidation potentials. Cyclic voltammetric and spectroelectrochemical studies allow differentiation between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these molecular assemblies. Transient absorption measurements give insight into the excited-state events and deliver corresponding kinetic data. Femtosecond transient absorption spectra in benzonitrile may suggest the occurrence of fast charge separation from TTF to porphyrin in dyads 2?a,b but not in triads 1?ac. Clear evidence for a photoinduced and relatively long lived charge-separated state (385 ps lifetime) is obtained for a supramolecular coordination compound built from the ZnPTTF dyad and a pyridine-functionalized C60 acceptor unit. This specific excited state results in a (ZnPTTF).+...(C60py).- state. The binding constant of ZnII...py is evaluated by constructing a BenesiHildebrand plot based on fluorescence data. This plot yields a binding constant K of 7.20X104?M-1, which is remarkably high for bonding of pyridine to ZnP.
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