From Linear to Angular Isomers: Achieving Tunable Charge Transport in Single-Crystal Indolocarbazoles Through Delicate Synergetic CH/NH⋅⋅⋅π Interactions
From Linear to Angular Isomers: Achieving Tunable Charge Transport in Single-Crystal Indolocarbazoles Through Delicate Synergetic CH/NH⋅⋅⋅π Interactions
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从线性异构体到角异构体：通过微妙的协同CH/NH相互作用实现单晶吲哚并咔唑中可调节的电荷传输
DOI：
10.1002/ange.201713288
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发表时间：
2018
影响因子：
--
通讯作者：
Wenping Hu
中科院分区：
文献类型：
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作者：
Hui Jiang;Peng Hu;Jun Ye;Apoorva Chaturvedi;Keke K. Zhang;Yongxin Li;Yi Long;Denis Fichou;Christian Kloc;Wenping Hu
有机半导体分子晶体中的弱分子间相互作用对分子堆积和电子性质有重要影响。在这里，我们合理地设计和合成了四个五环稠合异构体，考察了线型和角型异构体对分子堆积和电子性质的影响。单晶场效应晶体管的迁移率顺序为5，7-ICZ(3.61 cm2V−1S−1)和GT；5，11-ICZ(0.55 cm2V−1S−1)和GT；11，12-ICZ(约10−5cm2V−1S−1)和5，12-ICZ(约10−6cm2V−1S−1)。基于密度泛函理论和极化子输运模型的理论计算表明，5，7-ICZ可以达到较高的迁移率，这是因为相对较高的空穴转移积分，由于存在多个NH⋅⋅⋅π和CH⋅⋅⋅π(Py)相互作用而导致较强的分子间相互作用，这些相互作用的能量接近共同的NH⋅⋅⋅N氢键，以及由于较好的π共轭而没有空穴与低频模式的耦合而导致整体较低的空穴-振动耦合。
Weak intermolecular interaction in organic semiconducting molecular crystals plays an important role in molecular packing and electronic properties. Here, four five‐ring‐fused isomers were rationally designed and synthesized to investigate the isomeric influence of linear and angular shapes in affecting their molecular packing and resultant electronic properties. Single‐crystal field‐effect transistors showed mobility order of 5,7‐ICZ (3.61 cm2V−1s−1) >5,11‐ICZ (0.55 cm2V−1s−1) >11,12‐ICZ (ca. 10−5cm2V−1s−1) and 5,12‐ICZ (ca. 10−6cm2V−1s−1). Theoretical calculations based on density functional theory (DFT) and polaron transport model revealed that 5,7‐ICZ can reach higher mobilities than the others thanks to relatively higher hole transfer integral that links to stronger intermolecular interaction due to the presence of multiple NH⋅⋅⋅π and CH⋅⋅⋅π(py) interactions with energy close to common NH⋅⋅⋅N hydrogen bonds, as well as overall lower hole‐vibrational coupling owing to the absence of coupling of holes to low frequency modes due to better π conjugation.