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Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High‐Spin Molecules
Author(s) -
Kolanji Kubandiran,
Baumgarten Martin
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.201905734
Subject(s) - dication , chemistry , electron paramagnetic resonance , cyclic voltammetry , radical , molecule , cationic polymerization , radical ion , nitroxide mediated radical polymerization , pyrrole , photochemistry , electrochemistry , spectroscopy , medicinal chemistry , polymerization , polymer chemistry , ion , organic chemistry , radical polymerization , polymer , physics , electrode , nuclear magnetic resonance , quantum mechanics
Three 1 N‐phenyl nitronyl nitroxide (NN) 4‐substituted dithieno[3,2‐ b :2′,3′‐ d ]pyrrole ( DTP ) derivatives with R 1=4‐phenyl‐, 4H‐, and 4‐methylthiothiophenyl‐ ( R 1 2 DTP‐Ph‐NN , R 1 =H, Ph and MeSTh) were designed, synthesized and characterized. The electrochemical properties were studied by cyclic voltammetry (CV). All the molecules exhibited two main oxidation peaks, first for radical cation and next for dication formation. The cation and dication formation were also confirmed by UV/Vis absorption spectroscopy for Ph 2 DTP‐Ph‐NN and MeSTh 2 DTP‐Ph‐NN titrated with tris (4‐bromophenyl)aminiumhexachloroantimonate (magic blue). In addition, the cation and dication formation were verified by EPR spectroscopy. Finally, the exchange interactions ( J/k B ) of NN and radical cation were calculated by DFT studies.