Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/10978
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dc.contributor.authorNgo, Thien H.-
dc.contributor.authorPuntoriero, Fausto-
dc.contributor.authorNastasi, Francesco-
dc.contributor.authorRobeyns, Koen-
dc.contributor.authorVan Meervelt, Luc-
dc.contributor.authorCampagna, Sebastian-
dc.contributor.authorDehaen, Wim-
dc.contributor.authorMAES, Wouter-
dc.date.accessioned2010-07-06T07:43:45Z-
dc.date.availableNO_RESTRICTION-
dc.date.available2010-07-06T07:43:45Z-
dc.date.issued2010-
dc.identifier.citationCHEMISTRY-A EUROPEAN JOURNAL, 16(19). p. 5691-5705-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/1942/10978-
dc.description.abstractmeso-Pyrimidinyl-substituted AB(2)-corroles were efficiently synthesized starting from 5-mesityldipyrromethane and various 2-substituted 4,6-dichloropyrimidine-5-carbaldehydes. The corrole yield was significantly enhanced by optimization of the amount of Lewis acid catalyst (BF3 center dot OEt2). The main advantage of pyrimidinylcorroles over other meso-triarylcorroles is their wide range of functionalization possibilities, which has been explored by nucleophilic and electrophilic aromatic substitution, and Pd-catalyzed cross-coupling reactions. Stepwise substitution of the chlorine functions afforded asymmetrically substituted pyrimidinylcorroles. Due to the lability of the free-base corrole macrocycles, functionalization of the corrole periphery was preferentially performed on the Cu-metalated counterparts. Functionalized free-base AB(2)-pyrimidinylcorroles were, however, readily accessible by the reversible sequence Cu insertion and subsequent reductive demetalation. AB(2)-pyrimidinylcorroles can hence be regarded as highly versatile platforms towards more sophisticated corrole systems. X-ray analysis of a bis(4-tert-butylphenoxy)-substituted Cu-pyrimidinylcorrole showed the typical features of a Cu corrole: short N-Cu distances and a saddled corrole plane. The absorption spectra and photophysical properties of some representative free-base AB(2)-pyrimidinylcorroles were examined in depth. The absorption spectra displayed typical corrole features: intense spin-allowed pi-pi* bands, which can be classified as Soret- and Q-type bands. The photophysical properties, investigated both in fluid solution at room temperature and in rigid matrix at 77 K. were governed by the lowest-lying pi-pi* singlet state: however, in most cases, a state with partial charge-transfer character (from the corrole ring to the pyrimidinyli group) was proposed to contribute to the dynamic Properties of the emissive level.-
dc.description.sponsorshipThe authors thank the IWT (Institute for the Promotion of Innovation through Science and Technology in Flanders) for a doctoral fellowship to T.H.N., the FWO (Fund for Scientific Research Flanders) for financial support and a postdoctoral fellowship to W.M., and the KU Leuven and the Ministerie voor Wetenschapsbeleid for continuing financial support. The University of Messina (Progetti di Ricerca di Ateneo) is also acknowledged for financial support.-
dc.language.isoen-
dc.publisherWILEY-V C H VERLAG GMBH-
dc.subject.othercharge transfer; corroles; luminescence; pyrimidines; UV/Vis spectroscopy-
dc.titleSynthetic, Structural, and Photophysical Exploration of meso-Pyrimidinyl-Substituted AB(2)-Corroles-
dc.typeJournal Contribution-
dc.identifier.epage5705-
dc.identifier.issue19-
dc.identifier.spage5691-
dc.identifier.volume16-
local.format.pages15-
local.bibliographicCitation.jcatA1-
dc.description.notes[Ngo, Thien H.; Robeyns, Koen; Van Meervelt, Luc; Dehaen, Wim; Maes, Wouter] Katholieke Univ Leuven, Dept Chem, B-3001 Louvain, Belgium. [Puntoriero, Fausto; Nastasi, Francesco; Campagna, Sebastian] Univ Messina, Dipartimento Chim Inorgan Chim Analit & Chim Fis, Ctr Interuniv Convers Chim Energia Solare, I-98166 Messina, Italy. [Maes, Wouter] Hasselt Univ, Inst Mat Res IMO, Res Grp Organ & BioPolymer Chem, B-3590 Diepenbeek, Belgium. fpuntoriero@unime.it; wim.dehaen@chem.kuleuven.be-
local.type.refereedRefereed-
local.type.specifiedArticle-
dc.bibliographicCitation.oldjcatA1-
dc.identifier.doi10.1002/chem.201000008-
dc.identifier.isi000278349700023-
item.accessRightsRestricted Access-
item.contributorNgo, Thien H.-
item.contributorPuntoriero, Fausto-
item.contributorNastasi, Francesco-
item.contributorRobeyns, Koen-
item.contributorVan Meervelt, Luc-
item.contributorCampagna, Sebastian-
item.contributorDehaen, Wim-
item.contributorMAES, Wouter-
item.validationecoom 2011-
item.fulltextWith Fulltext-
item.fullcitationNgo, Thien H.; Puntoriero, Fausto; Nastasi, Francesco; Robeyns, Koen; Van Meervelt, Luc; Campagna, Sebastian; Dehaen, Wim & MAES, Wouter (2010) Synthetic, Structural, and Photophysical Exploration of meso-Pyrimidinyl-Substituted AB(2)-Corroles. In: CHEMISTRY-A EUROPEAN JOURNAL, 16(19). p. 5691-5705.-
crisitem.journal.issn0947-6539-
crisitem.journal.eissn1521-3765-
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