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首页> 外文期刊>Chemistry: A European journal >Homoleptic copper(I) arylthiolates as a new class of p-type charge carriers: Structures and charge mobility studies
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Homoleptic copper(I) arylthiolates as a new class of p-type charge carriers: Structures and charge mobility studies

机译：均一的芳基铜（I）芳硫醇盐类作为新型p型载流子：结构和电荷迁移率研究

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Polymeric homoleptic copper(I) arylthiolates [Cu(p-SC6H4-X)](infinity) (X=CH3 (1), H (2), CH3O (3), tBu (4), CF, (5), NO2 (6), and COOH (7)) have been prepared as insoluble crystalline solids in good yields (75-95 %). Structure determinations by powder X-ray diffraction analysis have revealed that 1-3 and 6 form polymers of infinite chain length, with the copper atoms bridged by arylthiolate ligands. Weak intra-chain pi center dot center dot center dot pi stacking interactions are present in 1-3, as evidenced by the distances (3.210 angstrom in 1, 3.016 angstrom in 2, 3.401 angstrom in 3) between the mean planes of neighboring phenyl rings. In the structure of 6, the intra-chain pi center dot center dot center dot pi interactions (d=3.711 angstrom) are insignificant and the chain polymers are associated through weak, non-covalent C-H center dot center dot center dot O hydrogen-bonding interactions (d = 2.586 angstrom). Samples of 1-7 in their polycrystalline forms proved to be thermally stable at 200-300 degrees C; their respective decomposition temperatures are around 100 degrees C higher than that of the aliphatic analogue [Cu(SCH3)](infinity). Data from in situ variable-temperature X-ray diffractometry measurements indicated that the structures of both 1 and 7 are thermally more robust than that of [Cu(SCH3)](infinity). TEM analysis revealed that the solid samples of 1-5 and [Cu(SCH3)](infinity) contained homogeneously dispersed crystalline nanorods with widths of 20-250 nm, whereas smaller plate-like nanocrystals were found for 6 and 7. SAED data showed that the chain polymers of 1-3 and [Cu(SCH3)](infinity) similarly extend along the long axes of their nanorods. The nanorods of 1-5 and [Cu(SCH3)](infinity) have been found to exhibit p-type field-effect transistor behavior, with charge mobility (mu) values of 10(-2)-10(-5) cm(2) V-1 s(-1). Polycrystalline solid samples of 6 and 7 each showed a low charge mobility (< 10(-6) cm(2) V-1 s(-1)). The charge mobility values of field-effect transistors made from crystalline nanorods of 1-3 and [Cu(SCH3)](infinity) could be correlated with their unique chain-like copper-sulfur networks, with the para-substituent of the arylthiolate ligand influencing the charge -transport properties.
机译：聚合均相芳基硫醇铜（I）[Cu（p-SC6H4-X）] [无穷大）（X = CH3（1），H（2），CH3O（3），tBu（4），CF，（5），NO2 （6）和COOH（7））已制备成不溶的结晶固体，收率良好（75-95％）。通过粉末X射线衍射分析的结构确定已经揭示1-3和6形成具有无限链长的聚合物，其中铜原子被芳基硫醇盐配体桥接。弱的链内pi中心点中心点中心点pi堆积相互作用存在于1-3中，这由相邻苯环的平均平面之间的距离（3.210埃在1，3.016埃在2，3,401埃在3中）证​​明了。在结构6中，链内pi中心点中心点中心点pi相互作用（d = 3.711埃）微不足道，并且链聚合物通过弱的，非共价的CH中心点中心点中心点中心氢键缔合相互作用（d = 2.586埃）。 1-7的多晶形式样品在200-300摄氏度下证明是热稳定的。它们各自的分解温度比脂族类似物[Cu（SCH3）]（无穷大）高约100摄氏度。来自原位可变温度X射线衍射测量的数据表明，1和7的结构都比[Cu（SCH3）] [infinity]具有更强的热稳定性。 TEM分析显示，固体样品1-5和[Cu（SCH3）]（无穷大）包含均匀分散的晶体纳米棒，其宽度为20-250 nm，而发现较小的板状纳米晶体为6和7。SAED数据显示1-3和[Cu（SCH3）]（无穷大）的链状聚合物类似地沿其纳米棒的长轴延伸。已发现1-5和[Cu（SCH3）] [infinity）的纳米棒表现出p型场效应晶体管行为，电荷迁移率（mu）值为10（-2）-10（-5）cm （2）V-1 s（-1）。 6和7的多晶固体样品均显示出低电荷迁移率（<10（-6）cm（2）V-1 s（-1））。由1-3和[Cu（SCH3）]（无穷大）的晶体纳米棒制成的场效应晶体管的电荷迁移率值可能与它们独特的链状铜-硫网络以及芳基硫醇盐配体的对位取代相关影响电荷传输性质。

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