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Volumn 128, Issue 47, 2006, Pages 15145-15154

Supramolecular bis(rutheniumphthalocyanine)-perylenediimide ensembles: Simple complexation as a powerful tool toward long-lived radical ion pair states

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; ELECTRONS; NITROGEN COMPOUNDS; REDUCTION; RUTHENIUM COMPOUNDS; SPECTROSCOPIC ANALYSIS;

EID: 33845338461     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0622195     Document Type: Article
Times cited : (144)

References (108)
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    • Perylenediimides possess two distinct chemical zones, namely the bay region and imido position, that can be easily functionalized independently one from the other. Thus, this kind of dye is ideally suited for the modular construction of geometrically diverse molecular and supramolecular architectures. For example, see: ref 19c and also (a) Würthner, F.; Sautter, A.; Schmid, D.; Weber, P. J. A. Chem. - Eur. J. 2001, 7, 894-902
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    • For some recent examples, see: ref 19d and also
    • Some porphyrin-perylenediimide arrays have been reported and studied for photoinduced electron-transfer processes. For some recent examples, see: ref 19d and also (a) Prodi, A.; Chiorboli, C.; Scandola, F.; Lengo, E.; Alessio, E.; Dobrawa, R.; Würthner, F. J. Am. Chem. Soc. 2005, 127, 1454-1562.
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    • See: refs 18, 22a and also
    • Despite the strength of Ru-pyridyl coordination bonds, in this kind of array the pyridyl substituents, and hence the phthalocyanine moieties, are electronically decoupled from the perylenediimide counterpart, due to the presence of nodes at the imido nitrogens in the HOMO and LUMO of this red chromophore. See: refs 18, 22a and also Mercadante, R.; Trsic, M.; Duff, J.; Aroca, R. THEOCHEM 1997, 394, 215-226.
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    • note
    • max = 348 and 678 nm, respectively.
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    • note
    • The remarkable difference in fluorescence quenching relates to the different fluorescence lifetimes that [BPyPDI] 3 and (Ru(CO)Pc] 2 exhibit.
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    • note
    • Despite the large driving force for charge separation, especially evolving from photoexcited [BPyPDI], no additional emission that might be attributable to a charge transfer is seen in the recorded range of up to 900 nm.
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    • note
    • Considering, however, that the [BPyPDIl triplet excited state lifetime is intrinsically shorter than that of the corresponding radical ion pair state, it might be populated but would be spectroscopically invisible to us.
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    • note
    • The [Ru(CO)Pc] triplet excited state is approximated as 1.14 eV, when considering the same singlet-triplet energy gap in ZnPc, but accounting tor a [Ru(CO)Pc] singlet excited state (1.87 eV) that is 007 eV higher than that of ZnPc (see ref 11h).


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