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Titolo:
Photoinduced energy and electron transfer in bis-porphyrins with quinoxaline Troger's base and biquinoxalinyl spacers
Autore:
Yeow, EKL; Sintic, PJ; Cabral, NM; Reek, JNH; Crossley, MJ; Ghiggino, KP;
Indirizzi:
Univ Melbourne, Sch Chem, Photophys Lab, Melbourne, Vic 3010, Australia Univ Melbourne Melbourne Vic Australia 3010 elbourne, Vic 3010, Australia Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia Univ Sydney Sydney NSWAustralia 2006 h Chem, Sydney, NSW 2006, Australia
Titolo Testata:
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
fascicolo: 19, volume: 2, anno: 2000,
pagine: 4281 - 4291
SICI:
1463-9076(2000)2:19<4281:PEAETI>2.0.ZU;2-M
Fonte:
ISI
Lingua:
ENG
Soggetto:
COVALENTLY-LINKED PORPHYRIN; EXCITON RESONANCE INTERACTIONS; PHOTOSYNTHETIC MODEL SYSTEMS; EXCITATION TRANSFER; AB-INITIO; 2-SUBSTITUTED 5,10,15,20-TETRAPHENYLPORPHYRINS; RHODOBACTER-SPHAEROIDES; HYBRID DIPORPHYRINS; REACTION CENTERS; RATE EXPRESSIONS;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
85
Recensione:
Indirizzi per estratti:
Indirizzo: Ghiggino, KP Univ Melbourne, Sch Chem, Photophys Lab, Melbourne, Vic 3010,Australia Univ Melbourne Melbourne Vic Australia 3010 3010, Australia
Citazione:
E.K.L. Yeow et al., "Photoinduced energy and electron transfer in bis-porphyrins with quinoxaline Troger's base and biquinoxalinyl spacers", PHYS CHEM P, 2(19), 2000, pp. 4281-4291

Abstract

The photophysical characterisation of bis-porphyrins consisting of two porphyrins bridged by either a quinoxaline Troger's base (1 and 2) or a biquinoxalinyl (3) spacer are reported. Efficient intramolecular electronic energy transfer (EET) between the rigidly linked free-base porphyrins in 1 and from the zinc(ii) porphyrin to the free-base porphyrin in 2 has been investigated by steady-state absorption and emission spectroscopy, time-resolved fluorescence spectroscopy and semi-empirical calculations. A resonance dipole-dipole mechanism alone cannot account for the rate of EET in both 1 and 2. It is demonstrated that a superexchange mechanism via the quinoxaline Troger's base linker is responsible for the enhanced energy transfer rates in these systems. Strong quenching of the fluorescence intensity observed in 3is interpreted as arising from long-range (> 18 Angstrom) through-biquinoxalinyl bridge mediated photoinduced electron transfer from the free-base porphyrin to the gold(iii) porphyrin. These systems provide useful models forthe arrangements of the primary donor-acceptor pair in photosynthetic reaction centres, and for elucidating the role of the connecting bridge in electron and energy transfer processes.

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Documento generato il 26/09/20 alle ore 14:22:38