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Electron‐Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines
Author(s) -
May Lars,
Müller Thomas J. J.
Publication year - 2020
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.202000137
Subject(s) - phenothiazine , thiophene , intramolecular force , delocalized electron , thiazine , annulene , chemistry , cyclic voltammetry , intermolecular force , electron delocalization , electrochemistry , photochemistry , alkoxy group , computational chemistry , molecule , stereochemistry , organic chemistry , medicine , alkyl , electrode , pharmacology
A series of isomeric dithieno[1,4]thiazines is accessible through an intermolecular–intramolecular Buchwald–Hartwig amination starting from dihalodithienyl sulfides. The electronic properties of dithieno[1,4]thiazine isomers differ conspicuously over a broad range depending on the thiophene–thiazine anellation: a large cathodic (340 mV) or an anodic shift (130 mV) of the redox potentials relative to corresponding phenothiazines is possible. Structure–property relationships of the dithieno[1,4]thiazine constitution derived from DFT calculations and cyclic voltammetry not only reveal increased electron density but also different delocalization of the radical cations that determines the electrochemical properties significantly. In addition, photophysical properties (absorption and emission) qualify dithieno[1,4]thiazines as promising substitutes of phenothiazine and beyond due to increased tunable electron richness.