Document Detail


Synthetic, structural, and photophysical exploration of meso-pyrimidinyl-substituted AB2-corroles.
MedLine Citation:
PMID:  20394086     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
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 (BF(3).OEt(2)). 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 pyrimidinyl group) was proposed to contribute to the dynamic properties of the emissive level.
Authors:
Thien H Ngo; Fausto Puntoriero; Francesco Nastasi; Koen Robeyns; Luc Van Meervelt; Sebastiano Campagna; Wim Dehaen; Wouter Maes
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  16     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2010 May 
Date Detail:
Created Date:  2010-05-17     Completed Date:  2010-08-10     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  5691-705     Citation Subset:  IM    
Affiliation:
Molecular Design and Synthesis, Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
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MeSH Terms
Descriptor/Qualifier:
Catalysis
Cross-Linking Reagents
Luminescence
Metals / chemistry*
Molecular Structure
Photolysis
Porphyrins / chemical synthesis*,  chemistry
Pyrimidines / chemical synthesis*,  chemistry*
Quantum Theory
Solutions
Spectrophotometry, Ultraviolet
Chemical
Reg. No./Substance:
0/Cross-Linking Reagents; 0/Metals; 0/Porphyrins; 0/Pyrimidines; 0/Solutions; 0/corrole

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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