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Parent, Unsubstituted Corrphycene: Synthesis and Properties
Author(s) -
Listkowski Arkadiusz,
Piechocka Magdalena,
Kijak Michał,
RybakiewiczSekita Renata,
Luboradzki Roman,
Waluk Jacek
Publication year - 2025
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.202500779
Abstract We report the synthesis of a porphyrin isomer that, until now, has only been obtained in the form of multiply substituted derivatives. Structural, spectral, and electrochemical characteristics of unsubstituted corrphycene ( Cp ) are described along with the data for its precursor, 11,18‐di‐ tert ‐butylcorrphycene. Similar to porphine, Cp turns out to be a soft chromophore, characterized by very similar energy splittings between the pairs of frontier HOMO and LUMO orbitals. Magnetic circular dichroism spectra indicate that the splitting in the HOMO orbitals is larger than in the LUMO, opposite to the DFT predictions. Corrphycene exists in the form of a doubly degenerate trans tautomeric species. The two intramolecular H‐bonds are not equivalent, which strongly suggests a stepwise mechanism of trans‐trans conversion. Being a nearly perfect soft chromophore, Cp emerges as an attractive candidate for sensing changes in its environment.