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Crystal Engineering Using Polyiodide Halogen and Chalcogen Bonding to Isolate the Phenothiazinium Radical Cation and Its Rare Dimer, 10‐(3‐Phenothiazinylidene)phenothiazinium
Author(s) -
Peloquin Andrew J.,
McMillen Colin D.,
Iacono Scott T.,
Pennington William T.
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.202100730
Subject(s) - chemistry , dimer , iodide , chalcogen , photochemistry , radical ion , halogen , crystal structure , phenothiazine , hydrogen bond , cationic polymerization , halide , medicinal chemistry , crystallography , polymer chemistry , molecule , organic chemistry , ion , medicine , alkyl , pharmacology
Utilizing facile one‐electron oxidation of 10H‐phenothiazine by molecular diiodine, the solid‐state structure of the 10H‐phenothiazinium radical cation was obtained in three cation:iodide ratios, as well as its THF and acetone solvates. Oxidation of 10H‐phenothiazine with molecular diiodine in DMSO or DMF provided the structure of the radical coupling product 10‐(3‐phenothiazinyldene)phenothiazinium, which has not been crystallographically characterized to date. The radical cations were balanced by a mixture (I 7 ) − , (I 5 ) − , (I 3 ) − , and I − anions, where a variety of chalcogen, halogen, and hydrogen bonding interactions stabilize the structures to reveal these interesting cationic species.