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Title: | Corrole-Porphyrin Conjugates with Interchangeable Metal Centers | Authors: | Ngo, Thien H. Nastasi, Francesco Puntoriero, Fausto Campagna, Sebastiano Dehaen, Wim MAES, Wouter |
Issue Date: | 2012 | Publisher: | WILEY-V C H VERLAG GMBH | Source: | EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (28), p. 5605-5617 | Abstract: | Oligoporphyrinoid materials composed of two or three tetrapyrrolic macrocycles have been synthesized by either mono- or disubstitution (SNAr) of a phenolic Zn-AB3-porphyrin on a meso-dichloropyrimidinyl-substituted Cu-AB2-corrole. Selective metallation/demetallation sequences were carried out on these mixed corroleporphyrin conjugates to afford multichromophoric systems with variable metal centers. The absorption spectra of the free-base corroleporphyrin systems were essentially additive, which demonstrates that only weak intercomponent interactions take place in these assemblies and therefore they can be regarded as supramolecular systems. Photophysical studies of the free-base conjugates showed that these species are highly fluorescent, with fluorescence occurring from the lowest-energy singlet state of the porphyrin subunit(s), which is (are) the lowest-energy state(s) of the assemblies. Pump-probe transient absorption spectroscopy experiments demonstrated that very efficient (>95?%) corrole-to-porphyrin singletsinglet energy transfer takes place in these pyrimidinyl-bridged multichromophoric systems by a coulombic mechanism with rate constants on the picosecond timescale. | Notes: | [Nastasi, Francesco; Puntoriero, Fausto; Campagna, Sebastiano] Univ Messina, Dipartimento Chim Inorgan Chim Analit & Chim Fis, I-98166 Messina, Italy. [Nastasi, Francesco; Puntoriero, Fausto; Campagna, Sebastiano] Ctr Interuniv Convers Chim Energia Solare SOLAR C, I-98166 Messina, Italy. [Ngo, Thien H.; Dehaen, Wim; Maes, Wouter] Katholieke Univ Leuven, Dept Chem, B-3001 Louvain, Belgium. [Ngo, Thien H.] Free Univ Berlin, Inst Chem & Biochem Organ Chem, D-14195 Berlin, Germany. [Maes, Wouter] Hasselt Univ, Inst Mat Res IMO IMOMEC, B-3590 Diepenbeek, Belgium. campagna@unime.it; wouter.maes@uhasselt.be | Keywords: | Porphyrinoids; Macromo-lecules; Energy transfer; Chromophores; UV; Vis spectroscopy;Chemistry, Organic; porphyrinoids; macromolecules; energy transfer; chromophores; UV/Vis spectroscopy | Document URI: | http://hdl.handle.net/1942/14296 | ISSN: | 1434-193X | e-ISSN: | 1099-0690 | DOI: | 10.1002/ejoc.201200836 | ISI #: | 000308939800020 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2013 |
Appears in Collections: | Research publications |
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