title: meso-Ester Corroles.
abstract: 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.
authors: Aix Marseille Université, CNRS UMR 7325, Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), 13288 Marseille (France), Fax: (+33) 491-41-8916 http://www.cinam.univ-mrs.fr. gabriel.canard@univ-amu.fr.
authors: Gabriel
authors: G
authors: Canard
authors: Di
authors: D
authors: Gao
authors: Anthony
authors: A
authors: D'Aléo
authors: Michel
authors: M
authors: Giorgi
authors: Florian-Xuan
authors: FX
authors: Dang
authors: Teodor Silviu
authors: TS
authors: Balaban
keywords: corroles; electrochemistry; esters; luminescence; porphyrinoids