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Photophysics of novel 22π porphyrinoids

Max-Planck-Institut für Bioanorganische Chemie (formerly für Strahlenchemie), Postfach 10 13 65, D-45413 Mülheim an der Ruhr, Germany

Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CCT-La Plata-CONICET, Universidad Nacional de La Plata, La Plata, Argentina

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Sigrid Russell

Max-Planck-Institut für Bioanorganische Chemie (formerly für Strahlenchemie), Postfach 10 13 65, D-45413 Mülheim an der Ruhr, Germany

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Hans-Jürgen Dietrich

Institut für Organische Chemie, Universität Köln, Greinstrasse 4, D-50939 Köln, Germany

Current address: BASF IT Services GmbH, Ludwigshafen, Germany.

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Carlos J. Cobos

Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CCT-La Plata-CONICET, Universidad Nacional de La Plata, La Plata, Argentina

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, and

Silvia E. Braslavsky

Max-Planck-Institut für Bioanorganische Chemie (formerly für Strahlenchemie), Postfach 10 13 65, D-45413 Mülheim an der Ruhr, Germany

Corresponding author, fax: +49 (208)-306-3951.

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https://doi.org/10.1142/S1088424612500496Cited by:1 (Source: Crossref)

Abstract

The photophysical properties of toluene solutions of two new 22π expanded porphycene compounds were measured using a combination of various steady-state and time-resolved techniques. The determined triplet energy (E_T= 109 ± 3) kJ.mol^-1, coincident with the calculated E_T = (96.0 ± 10) kJ.mol^-1, of both red absorbing compounds is higher than the energy required to excite ground state molecular oxygen to singlet molecular oxygen. However, the intersystem crossing yield is very low (ca. 10^-2), which makes these compounds poor photosensitizers. The triplet state yield of the two expanded 22π porphyrinoid compounds is much lower than that of the parent porphycene, whereas their fluorescence is as high (ca. 30%) as the value for porphycene. The slower than diffusional quenching rate constant of a porphycene triplet state by the two new compounds reflects a steric hindering factor of the exothermic energy transfer.

Dedicated to Professor Emanuel Vogel in memoriam

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