http://www.cnr.it/ontology/cnr/individuo/prodotto/ID184503
Relaxation Properties of Porphyrin, Diprotonated Porphyrin, and Isoelectronic Tetraoxaporphyrin Dication in the S2 State (Articolo in rivista)
- Type
- Label
- Relaxation Properties of Porphyrin, Diprotonated Porphyrin, and Isoelectronic Tetraoxaporphyrin Dication in the S2 State (Articolo in rivista) (literal)
- Anno
- 2007-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1021/jp0686846 (literal)
- Alternative label
Agnese Marcelli; Paolo Foggi; Laura Moroni; Cristina Gellini; Pier Remigio Salvi; Ivana Jelovica Badovinac (2007)
Relaxation Properties of Porphyrin, Diprotonated Porphyrin, and Isoelectronic Tetraoxaporphyrin Dication in the S2 State
in The journal of physical chemistry. A
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- Agnese Marcelli; Paolo Foggi; Laura Moroni; Cristina Gellini; Pier Remigio Salvi; Ivana Jelovica Badovinac (literal)
- Pagina inizio
- Pagina fine
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
- Rivista
- Note
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
- Laboratorio Europeo di Spettroscopie non Lineari (LENS), Universita´ di Firenze;
Dipartimento di Chimica, Universita´ di Perugia;
INO-CNR
Dipartimento di Chimica, Universita´ di Firenze;
Faculty of Arts and Sciences, Physics Department, University of Rijeka (literal)
- Titolo
- Relaxation Properties of Porphyrin, Diprotonated Porphyrin, and Isoelectronic Tetraoxaporphyrin Dication in the S2 State (literal)
- Abstract
- The fluorescence spectra of unsubstituted porphyrin (H2P), diprotonated porphyrin (H4P2+), and isoelectronic
tetraoxaporphyrin dication (TOxP2+) have been measured in solution at room temperature. The S2 f S0
fluorescence has been observed, much more intense for TOxP2+ than for H4P2+ and H2P. In the TOxP2+ case,
the S2 f S0 fluorescence spectrum is remarkably sharp and shows an excellent mirror symmetry with respect
to S0 f S2 absorption. On the contrary, the spectra of H4P2+ and H2P are shifted and more extended with
respect to the absorption counterparts. The differences have been attributed primarily to the change of the
equilibrium geometry upon excitation, larger in H2P and H4P2+ than in TOxP2+ and in the case of H4P2+ to
the nonplanar conformation of the macrocycle. Also the S1 f S0 spectra of H2P, H4P2+, and TOxP2+ have
been measured and more qualitatively discussed. The S1 and S2 fluorescence decays have been observed for
H4P2+ and TOxP2+ exciting with ultrashort pulses. The S2 lifetime of TOxP2+ is of the order of the temporal
resolution of our experimental apparatus, whereas that of H4P2+ is shorter. The S2 f S0 quantum yield of
TOxP2+ has been estimated to be 0.035, ?3 orders of magnitude higher than that of H4P2+. It is proposed on
the basis of ab initio model calculations that excited states of the H4P2+(CF3COO-)2 complex with chargetransfer
character are responsible of the increased extension of the S2 f S0 spectrum with respect to that of
H2P. (literal)
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