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Zinc‐ and Cadmium meso ‐Aryl‐Isoporphyrins: Non‐Aromatic NIR Dyes with Distinct Conformational Features
Author(s) -
Baş Çağla,
Krumsieck Jens,
Möller WilliamDale,
Körner Dominik,
Bröring Martin
Publication year - 2021
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.202100686
Subject(s) - chemistry , atropisomer , intramolecular force , steric effects , diastereomer , aryl , zinc , reagent , electrochemistry , ligand (biochemistry) , stereochemistry , photochemistry , medicinal chemistry , organic chemistry , alkyl , biochemistry , receptor , electrode
Abstract A series of pyrrolyl and dipyrrinyl isoporphyrins carrying different phenyl and thienyl groups is reported. The compounds are obtained by a one‐pot approach in the presence of a template reagent. Thienyl derivatives gave better yields, and were the only subclass to form with steric hindrance. The structural analyses carried out on compounds 1 and 14 revealed distinct conformational differences which are likely to result from an intramolecular NH … Cl hydrogen bridge of the pyrrolyl subclass. In addition, this hydrogen bridge strongly favors one of the two possible atropisomers. Hindered rotation of the meso ‐aryl groups is observed only in the cases of methylbenzothienyl derivatives 10 and 15 and leads to the observation of several diastereomers. NIR absorptions up to 923 nm are found throughout. Electrochemical investigations into the 1e − and 2e − reduced species unravel axial ligand exchange dynamics for the zinc isoporphyrin radical, and the probable formation of a zinc phlorinate.