Ultrafast intramolecular charge transfer in tetrapyrazinoporphyrazines controls the quantum yields of fluorescence and singlet oxygen

0342767 - ÚACH 2011 RIV GB eng J - Článek v odborném periodiku
Nováková, V. - Zimčík, P. - Miletín, M. - Váchová, L. - Kopecký, K. - Lang, Kamil - Chábera, P. - Polívka, T.
Ultrafast intramolecular charge transfer in tetrapyrazinoporphyrazines controls the quantum yields of fluorescence and singlet oxygen.
Physical Chemistry Chemical Physics. Roč. 12, č. 11 (2010), s. 2555-2563. ISSN 1463-9076. E-ISSN 1463-9084
Grant CEP: GA ČR GA203/07/1424
Výzkumný záměr: CEZ:AV0Z40320502
Klíčová slova: photoinduced electron-transfer * phthalocyanine-fullerene ensembles * nonlinear-optical properties
Kód oboru RIV: CA - Anorganická chemie
Impakt faktor: 3.454, rok: 2010

A series of octasubstituted zinc(II) tetrapyrazinoporphyrazines (TPyzPz), aza-analogues of phthalocyanines, differing in the number of peripheral N,N-diethylamino (n = 0-8) and tert-butylsulfanyl substituents (m = 8 - n) has been synthesized. All possible congeners were characterized including adjacent and opposite isomers. Steady-state (UV-vis, fluorescence) and time-resolved (fluorescence, femtosecond transient absorption) spectroscopies, redox and photochemical (singlet oxygen formation) properties were investigated and compared. The peripheral tertiary amino substituents (donor) induce a new competitive relaxation pathway to fluorescence and intersystem crossing due to the mixing of the first excited state S-1 of the TPyzPz macrocycle with a nearby intramolecular charge transfer (ICT) state.
Trvalý link: http://hdl.handle.net/11104/0185403