Excellentπ-Bowl Semiconductors Based on C_(70)Subunit  

作　　者：Meng Chen Yuxiao Duan Xinyue Liu Qian Zhan Hironobu Hayashi Kyohei Matsuo Hiroko Yamada Guangpeng Gao Yonghao Zheng Lei Zhang 

机构地区：[1]Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing 100029 [2]School of Optoelectronic Science and Engineering,University of Electronic Science and Technology of China(UESTC),Chengdu 610054 [3]Division of Materials Science,Nara Institute of Science and Technology(NAIST),Ikoma,Nara 630-0192 [4]Key Laboratory of Cluster Science of Ministry of Education,Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials,School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 100081

出　　处：《CCS Chemistry》2024年第2期353-364,共12页中国化学会会刊（英文）

基　　金：support of the National Natural Science Foundation of China(NSFC)(grant nos.21871022,22005018,22175013);JSPS KAKENHI(grant nos.JP20H00379(H.Y.),JP20H05833(H.Y.),and JP20H02816(H.H.)).

摘　　要：As open substructures of fullerenes,aromaticπ-bowls are promising candidates as new organic semiconductors,as well as attractive hosts for fullerenes.We demonstrate herein the synthesis and characterization of a novel C_(2v)symmetricπ-bowl,pyracyleno[6,5,4,3,2,1-pqrstuv]pentaphene(3).Bowl 3 was equipped with two distinctive reactive sites,allowing for bromination and cross-coupling reactions to readily yield functionalized bowls with two 2,4,6-trimethylphenyl(5)and triethylsilyl(TES)-ethynyl(6)substituents,respectively.Variable-temperature 1H NMR analysis and density functional theory(DFT)calculations indicated bowl-to-bowl inversions of 3,5,and 6 at room temperature.By alternating the substituents,the crystal structures of the threeπ-bowls 3,5,and 6 could be controlled from 1D linear to 1D slipped to 2D herringbone packing motifs,providing insight into the packing behavior ofπ-bowls.1H NMR titration study indicated that the TES-ethynyl substituent enhanced the ability ofπ-bowl to bind C_(70)with an association constant of 2485 M−1.The C_(70)molecules withπ-bowls 3 and 6 formed 1:1 complexes,in which C_(70)molecules aggregated into zig-zag and 1D linear arrays,respectively.The hole mobility of 2.3 cm^(2)V^(−1)^s(−1)and electron mobility of 0.16 cm^(2)V^(−1)^s(−1)ofπ-bowl 3 and its complex with C_(70)were demonstrated,respectively,which proved a great value for the development of aromaticπ-bowl semiconductors with tunable properties for organic electronic devices.

关 键 词：organic semiconductor π-bowl FULLERENE crystal engineering mobility 

分 类 号：O62[理学—有机化学]