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Heterocorrole Conformations: Little Saddling, Much Ruffling
Author(s) -
Rösner Jörn,
Cordes Birte,
Bahnmüller Stefanie,
Homolya Gabor,
Sakow Dimitri,
Schweyen Peter,
Wicht Richard,
Bröring Martin
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201705551
Subject(s) - chemistry , crystallography , corrole , ionic radius , metal , ion , inorganic chemistry , organic chemistry
10‐Heterocorrole complexes with oxygen, sulfur, and selenium at position 10 of the macrocycle and with the divalent ions of nickel, copper, and palladium were prepared and investigated. The focus was set on the size adaptation and matching mechanisms of cavity size versus ionic radius in corrole‐type macrocycles. A full set of single‐crystal X‐ray analytical data revealed that in all but one case the N 4 binding site of the ring‐contracted tetrapyrrole was larger than necessary to bind the metal ion without deformation. In‐plane size adaptation through M−N bond‐length elongation by 2.5–3.2 % was effective, as well as pronounced out‐of‐plane ruffling of the macrocycle for those compounds with a more severe size mismatch. Such ruffling had been excluded for corroles previously, but is apparently the most efficient mechanism to adapt to small central ions.