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Title: Synthetic, Structural, and Photophysical Exploration of meso-Pyrimidinyl-Substituted AB(2)-Corroles
Authors: Ngo, Thien H.
Puntoriero, Fausto
Nastasi, Francesco
Robeyns, Koen
Van Meervelt, Luc
Campagna, Sebastian
Dehaen, Wim
MAES, Wouter 
Issue Date: 2010
Source: CHEMISTRY-A EUROPEAN JOURNAL, 16(19). p. 5691-5705
Abstract: meso-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.
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.;
Keywords: charge transfer; corroles; luminescence; pyrimidines; UV/Vis spectroscopy
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ISSN: 0947-6539
e-ISSN: 1521-3765
DOI: 10.1002/chem.201000008
ISI #: 000278349700023
Category: A1
Type: Journal Contribution
Validations: ecoom 2011
Appears in Collections:Research publications

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