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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/16695

Title: Molecular Structures and Absorption Spectra Assignment of Corrole NH Tautomers
Authors: Beenken, Wichard
Presselt, Martin
Ngo, Thien H.
Dehaen, Wim
MAES, Wouter
Kruk, Mikalai
Issue Date: 2014
Citation: JOURNAL OF PHYSICAL CHEMISTRY A, 118 (5), p. 862-871
Abstract: The individual absorption spectra of the two NH tautomers of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole are assigned on the basis of the Gouterman four-orbital model and a quantum chemical TD-DFT study. The assignment indicates that the red-shifted T1 tautomer is the one with protonated pyrrole nitrogen atoms N(21), N(22) and N(23), whereas the blue-shifted T2 tautomer has pyrrole nitrogen atoms N(21), N(22) and N(24) protonated. A wave-like nonplanar distortion of the macrocycle in the ground state is found for both NH tautomers, with the wave axis going through the pyrroles containing N(22) and N(24). The 7C plane determined by the least-squares distances to the carbon atoms C1, C4, C5, C6, C9, C16, and C19 is suggested as a mean corrole macrocycle plane for the analysis of out-of-plane distortions. The magnitude of these distortions is distinctly different for the two NH tautomers, leading to substantial perturbations of their acid–base properties, which are rationalized by the interplay of the degree of out-of-plane distortion of the macrocycle as a whole and the tendency of the pyrrole nitrogen atoms toward pyramidalization, with the former leading to a basicity increase whereas the latter enhances the acidity.
Notes: Beenken, W (reprint author), Ilmenau Univ Technol, Inst Phys, POB 100565, D-98684 Ilmenau, Germany. wichard.beenken@tu-ilmenau.de
URI: http://hdl.handle.net/1942/16695
DOI: 10.1021/jp411033h
ISI #: 000331153400009
ISSN: 1089-5639
Category: A1
Type: Journal Contribution
Validation: ecoom, 2015
Appears in Collections: Research publications

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