Abstract
Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent.
Highlights
Infinite face-to-face π-stacking formations are known to be important for electrical and magnetic conduction in charge-transfer (CT) complex[1,2,3,4,5,6], since research reveals electron can migrate across the chains in form of unpaired electron interchain transport[7,8]
Crystal structures, spectroscopic characterizations, and physical properties of 1,2,4,5-Tetrakis-(isopropylthio)benzene (TPB) and 1,2,4,5-Tetrakis(ethylthio)-benzene (TEB) radical cations with weakly coordinating anion SbF−6
The at −20 °C, and the details of the crystallographic data are shown in supsingle crystal X-ray diffraction reveals that TPB·+ has π-dimer structure
Summary
Infinite face-to-face π-stacking formations are known to be important for electrical and magnetic conduction in charge-transfer (CT) complex[1,2,3,4,5,6], since research reveals electron can migrate across the chains in form of unpaired electron interchain transport[7,8]. Owing to its intrinsic instability and difficulty of crystallization, no second example of π-stacked oxidized conjugated oligomers has been structurally characterized until we stabilized the conductive crystals of 4,4′-terphenyldiamine radical cations in 2012 by introducing the large π-conjugate system and weak coordinating anion (WCA) (Fig. 1)[11]. Conductive thiophene/phenylene co-oligomer and TTF radical cations have been stabilized by WCA recently (Fig. 1)[21,22,23,24]. These dramatic results led by S atoms enlighten us to study on the single phenyl substituted with alkylthio groups. The study of CT complex can be less dependent on the hard-soluble oligomers
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