Radical Cation Salts of 1,3,6,8‐Tetrakis(methylthio)‐pyrene—New Easily Accessible Compounds with High Electrical Conductivity and Excellent Stability

“Manipulation” of Crystal Structure by Methylthiolation Enabling Ultrahigh Mobility in a Pyrene‐Based Molecular Semiconductor

“…MT‐pyrene synthesized according to the reported procedure was carefully purified by multiple vacuum sublimation. [ 20 ] Long and thin plates of MT‐pyrene single crystals were obtained by physical vapor transport. [ 21 ] The crystal structure of MT‐pyrene shown in Figure is strikingly different from that of parent pyrene, which is known as the sandwich (or dimeric) herringbone structure, [ 22 ] where a pair of pyrene molecules form a π‐stacking dimer that packs into a herringbone‐like motif (vide infra).…”

“…MT‐pyrene was synthesized from 1,3,6,8‐tetrabromopyrene and sodium methanethiolate according to the reported procedure. [ 20 ] The crude product including a trace amount of 1‐bromo‐3,6,8‐tris(methylthio)pyrene was treated with lithium aluminum hydride in tetrahydrofuran (THF) to convert the impurity to 1,3,6‐tris(methylthio)pyrene, which was easily removed by sublimation, and the resulting product was purified by multiple train sublimation under vacuum. With the purified powder sample, single crystals were grown by the physical vapor transport technique under a flow of nitrogen carrier gas.…”

“…To embody this, we choose pyrene as the parent system, as its largely π‐extended molecular structure can have potential to bring effective orbital overlap through face‐to‐face molecular aggregation in the solid state, [ 18 ] though only limited pyrene derivatives known to date have shown decent carrier transport properties. [ 19 ] The target molecule in this study, 1,3,6,8‐tetrakis(methylthio)pyrene (MT‐pyrene, Figure 1), first reported in 1991, [ 20 ] has turned out to crystallize into a new type of brickwork structure. We describe here the characteristic crystal structure of MT‐pyrene caused by methylthiolation and the carrier transport properties elucidated by single‐crystal FETs (SC‐FETs).…”

Crystal Structures of (Pyrene)10(I3-)4(I2)10 and [1,3,6,8-Tetrakis(methylthio)pyrene]3(I3-)3(I2)7: Structural Trends in Fused Aromatic Polyiodides

“…Structure of [1,3,6,8-Tetrakis(methylthio)pyrene] 3 (I 3 - ) 3 (I 2 ) 7 , 2. The molecule 1,3,6,8-tetrakis(methylthio)pyrene, abbreviated here as TMT-pyrene, has been previously synthesized. , The triiodide salt of this compound has been prepared, and its crystal structure has been determined. This salt has a high electrical conductivity.…”

Thermal, Optical, Electrochemical Properties and Conductivity of Pyrene Monomers

“…Heywang et al synthesized and characterized a series of 1,3,6,8-tetrakis(alkylsulfanyl)pyrenes and measured their conductivities in crystal and pressed pellet in the ground and doped state. Conductivities from 0.025 to 550 S/cm were obtained with these compounds [28,29]. Effects of the counter ion and the length of the alkyl chain were studied in detail.…”