Synthesis, Electrochemical Reduction and Radical Anions of 2‐[Bis(4‐amino(nitro)phenyl)aminomethyl]‐9 H ‐thioxanthene‐9‐one Derivatives

2‐[Bis(4‐amino(nitro)phenyl)aminomethyl]‐9 H ‐thioxanthene‐9‐ones and their S‐oxide derivatives have been synthesized, and their electrochemical reduction (ECR) in N , N ‐dimethylformamide (DMF) and MeCN has been studied by cyclic voltammetry (CV). The thioxanthene‐9‐one group [Th(O)S] and thioxanth...

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Published in:European journal of organic chemistry 2018-07, Vol.2018 (26), p.3471-3480
Main Authors: Shundrina, Inna K., Odintsov, Danila S., Os'kina, Irina A., Irtegova, Irina G., Shundrin, Leonid A.
Format: Article
Language:English
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Summary:2‐[Bis(4‐amino(nitro)phenyl)aminomethyl]‐9 H ‐thioxanthene‐9‐ones and their S‐oxide derivatives have been synthesized, and their electrochemical reduction (ECR) in N , N ‐dimethylformamide (DMF) and MeCN has been studied by cyclic voltammetry (CV). The thioxanthene‐9‐one group [Th(O)S] and thioxanthene‐9‐one S‐dioxide group [Th(O)SO 2 ] determine the first one‐electron peak potentials of 2‐[bis(4‐aminophenyl)aminomethyl]‐9 H ‐Th(O)S/Th(O)SO 2 . The first peak potentials of the corresponding dinitro compounds are determined by the ratio of reduction potentials of bis(4‐nitrophenyl)amino and 9 H ‐thioxanthene‐9‐ones moieties. Radical anions (RA) of the synthesized compounds have been obtained by ECR in DMF and MeCN and characterized by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G/PCM level of theory. Th(O)S and Th(O)SO 2 groups are thermally stable up to 270 °C. The synthesized 2‐[bis(4‐aminophenyl)aminomethyl]‐9 H ‐Th(O)S/Th(O)SO 2 are electrochemically active monomers for subsequent synthesis of the corresponding electroactive polyimides with thioxanthene‐9‐one based pendant groups for their applications in the design of nonvolatile memory storage devices. The pendant groups are characterized by low redox potentials and reversibility towards electron transfer.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201800525