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meso ‐Ester Corroles
Author(s) -
Canard Gabriel,
Gao Di,
D'Aléo Anthony,
Giorgi Michel,
Dang FlorianXuan,
Balaban Teodor Silviu
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406369
Subject(s) - corrole , steric effects , moiety , chromophore , chemistry , intermolecular force , alkyl , aryl , tautomer , crystallography , electrochemistry , single crystal , crystal structure , absorption spectroscopy , photochemistry , polymer chemistry , molecule , stereochemistry , organic chemistry , electrode , physics , quantum mechanics
The introduction of ester groups on the 5‐ and 15‐ meso positions of corroles stabilizes them against oxidation and induces a redshift of their absorption and emission spectra. These effects are studied through the photophysical and electrochemical characterization of up to 16 different 5,15‐diester corroles, in which the third meso position is free or occupied by an aryl group, a long alkyl chain, or an ester moiety. Single‐crystal X‐ray structure analysis of five 5,15‐diestercorroles and DFT and time‐dependent DFT calculations show that the strong electron‐withdrawing character of the 5,15 ester substituents is reinforced by their π overlap with the macrocyclic aromatic system. The crystal packing of corroles 2 , 4 , 6 , 9 , and 15 features short distances between chromophores that are stacked into columns thanks to the low steric hindrance of meso ‐ester groups. This close packing is partially due to intermolecular interactions that involve inner hydrogen and nitrogen atoms, and thereby, stabilize a single, identical corrole tautomeric form.