Zheng Zhang, Weizhe Hu, Zhibo Liu, Yusuke Tsutsui, Yasujiro Murata, Shu Seki and Takashi Hirose*,
{"title":"由同手性端功能化螺旋烯组成的永久极性的面对面螺旋柱。","authors":"Zheng Zhang, Weizhe Hu, Zhibo Liu, Yusuke Tsutsui, Yasujiro Murata, Shu Seki and Takashi Hirose*, ","doi":"10.1021/jacs.5c08688","DOIUrl":null,"url":null,"abstract":"<p >Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their performance is anticipated to be strongly influenced by how they assemble in the solid state. However, strategies for controlling the packing structure─particularly in helically twisted π-conjugated molecules─remain limited. In this work, we achieved a homochiral face-to-face columnar packing arrangement for helicene derivatives by modifying their helical ends with 2,1,3-thiadiazole and phenanthrene-fused ring structures. Theoretical calculations suggested significantly strong intermolecular interactions in the face-to-face columnar arrangement (e.g., <i>E</i><sub>total</sub> = −113.9 kJ·mol<sup>–1</sup>), comparable to those observed in planar π-conjugated molecules, likely due to the large overlap area between adjacent helical molecules. Thiadiazole-fused derivative (<i>P</i>)-<b>TD[7]H</b> and phenanthrene-fused derivative (<i>M</i>)-<b>1</b>, with face-to-face columnar arrangements in the solid state, exhibited a photoconductivity maximum of ΦΣμ<sub>max</sub> = 1 × 10<sup>–5</sup> cm<sup>2</sup>·V<sup>–1</sup>·s<sup>–1</sup> as determined by the flash-photolysis time-resolved microwave conductivity method, confirming its potential as an organic semiconductor.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 29","pages":"25978–25989"},"PeriodicalIF":15.6000,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes\",\"authors\":\"Zheng Zhang, Weizhe Hu, Zhibo Liu, Yusuke Tsutsui, Yasujiro Murata, Shu Seki and Takashi Hirose*, \",\"doi\":\"10.1021/jacs.5c08688\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their performance is anticipated to be strongly influenced by how they assemble in the solid state. However, strategies for controlling the packing structure─particularly in helically twisted π-conjugated molecules─remain limited. In this work, we achieved a homochiral face-to-face columnar packing arrangement for helicene derivatives by modifying their helical ends with 2,1,3-thiadiazole and phenanthrene-fused ring structures. Theoretical calculations suggested significantly strong intermolecular interactions in the face-to-face columnar arrangement (e.g., <i>E</i><sub>total</sub> = −113.9 kJ·mol<sup>–1</sup>), comparable to those observed in planar π-conjugated molecules, likely due to the large overlap area between adjacent helical molecules. Thiadiazole-fused derivative (<i>P</i>)-<b>TD[7]H</b> and phenanthrene-fused derivative (<i>M</i>)-<b>1</b>, with face-to-face columnar arrangements in the solid state, exhibited a photoconductivity maximum of ΦΣμ<sub>max</sub> = 1 × 10<sup>–5</sup> cm<sup>2</sup>·V<sup>–1</sup>·s<sup>–1</sup> as determined by the flash-photolysis time-resolved microwave conductivity method, confirming its potential as an organic semiconductor.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"147 29\",\"pages\":\"25978–25989\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-07-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.5c08688\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.5c08688","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes
Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their performance is anticipated to be strongly influenced by how they assemble in the solid state. However, strategies for controlling the packing structure─particularly in helically twisted π-conjugated molecules─remain limited. In this work, we achieved a homochiral face-to-face columnar packing arrangement for helicene derivatives by modifying their helical ends with 2,1,3-thiadiazole and phenanthrene-fused ring structures. Theoretical calculations suggested significantly strong intermolecular interactions in the face-to-face columnar arrangement (e.g., Etotal = −113.9 kJ·mol–1), comparable to those observed in planar π-conjugated molecules, likely due to the large overlap area between adjacent helical molecules. Thiadiazole-fused derivative (P)-TD[7]H and phenanthrene-fused derivative (M)-1, with face-to-face columnar arrangements in the solid state, exhibited a photoconductivity maximum of ΦΣμmax = 1 × 10–5 cm2·V–1·s–1 as determined by the flash-photolysis time-resolved microwave conductivity method, confirming its potential as an organic semiconductor.
期刊介绍:
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