The bisporphyrin host ZnH was synthesized, and its complexation with two aromatic diimide guest molecules, bis(pyridyl)naphthalenediimide NIN and bis(pyridyl)phenyldiimide PIN, was investigated by H-1 NMR and UV/Vis spectroscopy. The diimide guests were complexed simultaneously with both metalloporphyrins of the host, with association constants on the order of 10(8) M-1. The processes occurring in the complex after excitation of the porphyrinic host were studied by steady-state and time-resolved emission and transient absorption spectroscopy. Complexation alters the photophysical properties of the host ZnH; the luminescence bands shift to the red by 30 nm in the complexed forms, while the emission quantum yield and the lifetime decrease. Comparison of a complex between ZnH and a model guest unable to undergo photoinduced processes allowed us to establish that, in the diimide complexes, quenching of the porphyrinic luminescence occurs with a rate of 1.1x10(10) s(-1). The process is identified as an electron transfer from the excited singlet of the porphyrinic host to the imide guest, which yields charge-separated states with a lifetime of 710 ps for ZnH+-NIN- and 260 ps for ZnH+-PIN-.

Photoinduced Electron Transfer in Bis-Porphyrin Di-imide Complexes

Flamigni L;
2002

Abstract

The bisporphyrin host ZnH was synthesized, and its complexation with two aromatic diimide guest molecules, bis(pyridyl)naphthalenediimide NIN and bis(pyridyl)phenyldiimide PIN, was investigated by H-1 NMR and UV/Vis spectroscopy. The diimide guests were complexed simultaneously with both metalloporphyrins of the host, with association constants on the order of 10(8) M-1. The processes occurring in the complex after excitation of the porphyrinic host were studied by steady-state and time-resolved emission and transient absorption spectroscopy. Complexation alters the photophysical properties of the host ZnH; the luminescence bands shift to the red by 30 nm in the complexed forms, while the emission quantum yield and the lifetime decrease. Comparison of a complex between ZnH and a model guest unable to undergo photoinduced processes allowed us to establish that, in the diimide complexes, quenching of the porphyrinic luminescence occurs with a rate of 1.1x10(10) s(-1). The process is identified as an electron transfer from the excited singlet of the porphyrinic host to the imide guest, which yields charge-separated states with a lifetime of 710 ps for ZnH+-NIN- and 260 ps for ZnH+-PIN-.
2002
Istituto per la Sintesi Organica e la Fotoreattivita' - ISOF
Porfirine
Chimica supramolecolare
Electron-transfer
Energy-transfer
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/36157
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