What Defines a Crystal Structure? Effects of Chalcogen Atoms in 3, <scp>7‐Bis</scp> (methylchalcogeno)benzo[1,2‐ <i>b</i> :4,5‐ <i>b</i> ′] <scp>dichalcogenophene‐Based</scp>
What Defines a Crystal Structure? Effects of Chalcogen Atoms in 3, <scp>7‐Bis</scp> (methylchalcogeno)benzo[1,2‐ <i>b</i> :4,5‐ <i>b</i> ′] <scp>dichalcogenophene‐Based</scp>
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什么定义了晶体结构？ 3, <scp>7-Bis</scp> (甲基硫属元素)苯并[1,2- <i>b</i> :4,5- <i>b< /i> ′] <scp>基于二硫族基因酚</scp>
DOI：
10.1002/cjoc.202200302
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发表时间：
2022
影响因子：
5.4
通讯作者：
Kawabata Kohsuke
中科院分区：
文献类型：
--
作者：
Takimiya Kazuo;Bulgarevich Kirill;Sahara Kamon;Kanazawa Kiseki;Takenaka Hiroyuki;Kawabata Kohsuke
为了了解硫族元素原子对3，7-双（甲基硫族元素）苯并[1，2-B：4，5-B′]二硫族化合物系列有机半导体晶体结构的影响，新合成了三种苯并二呋喃衍生物（1-3）以及苯并二噻吩和苯并二硒的二甲氧基衍生物（4和7），以完成氧-、硫-和硒-衍生物（1-9）的“3 × 3矩阵”。1 - 9的晶体结构分为四类，夹心倾斜π堆叠（1），二聚体（2和3），倾斜π堆叠（4，5，7，8，9）和砖结构（6和9）。通过理论计算，分析了不同硫族元素原子的晶体结构差异的原因，指出核中的硫族元素原子和取代基主要影响堆积结构。虽然在气相中的晶体生长提供不同的多晶型物，晶体结构和载流子输运性质之间的关系进行了仔细的研究。通过这些全面的评估，我们得出结论：i）甲基硫属元素化是改变堆积结构的有力工具，ii）每个甲基硫属元素基团具有其在很大程度上影响固态中分子间相互作用和电子结构的特征，以及iii）可结晶成适当间距的π堆叠结构的有机半导体作为FET应用的高性能活性材料是有希望的。
Comprehensive SummaryTo understand the effects of chalcogen atoms on the crystal structure of the series of 3,7‐bis(methylchalcogeno)benzo[1,2‐b:4,5‐b′]dichalcogenophene‐based organic semiconductors, three benzodifuran derivatives (1—3) and dimethoxy derivatives of benzodithiophene and benzodiselenophene (4and7) were newly synthesized to complete the “3 × 3 matrix” of the oxygen‐, sulfur‐, and selenium‐derivatives (1—9). The crystal structures of1—9were classified into four classes, sandwich pitched π‐stack (1), dimeric (2and3), pitched π‐stack (4,5,7,8,9), and brickwork structure (6and9). The causes for the different crystal structures depending on the chalcogen atoms were investigated by the theoretical calculations, indicating that the chalcogen atoms in the core and substituents primarily affected the packing structures. Although the crystal growth in the vapor phase afforded different polymorphs, the relationship between the crystal structure and the carrier transport property was carefully investigated. With these comprehensive evaluations, we conclude that; i) methylchalcogenolation is a powerful tool to alter the packing structure, ii) each methylchalcogeno group has its features that largely influence the intermolecular interaction and electronic structure in the solid state, and iii) organic semiconductors being crystallizable into appropriate pitched π‐stack structures are promising as high‐performance active materials for FET applications.