中国科学院上海有机化学研究所高希珂

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高希珂，现任中国科学院上海有机化学研究所研究员，隶属于中国科学院有机功能分子合成与组装化学重点实验室。2002年和2005年分别于聊城大学获得理学学士和硕士学位，2008于中国科学院化学研究所获理学博士学位。2008年10月-2014年2月，任上海有机所副研究员/课题组长（其中，2012年12月-2013年3月，在佐治亚理工学院访问交流）；2014年3月-至今，任上海有机所研究员/课题组长（入选所聘百人计划）。2011年入选上海市青年科技启明星计划和首批中科院青年创新促进会会员；2013年获中科院卢嘉锡青年人才奖；2015年获得国家优秀青年科学基金资助，入选中科院青年创新促进会首批优秀会员。


姓 名:高希珂        
性 别:男
职 称:研究员        
学 历:博士研究生
电 话:021-54925072        
传 真:021-64166128
电子邮件:gaoxk@mail.sioc.ac.cn        
个人主页:http://sacofm.sioc.ac.cn/gaoxike/china/homepage.asp
通讯地址:上海市零陵路345号　200032        

研究方向：
　　有机分子功能材料化学:
　　1. 新型共轭分子骨架的结构设计与合成
　　2. 有机共轭分子/高分子的合成方法
　　3. 有机共轭分子/高分子的组装与光电功能
专家类别：研究员,课题组长
职务：课题组长
获奖及荣誉：
代表论著：
　　1.Wenting Wu, Jing Li, Zheng Zhao, Xiaodi Yang, and Xike Gao.* Synthesis of largely π-extended naphthalenediimides via C–H activation towards highly soluble and narrow band-gap organic optoelectronic materials. Org. Chem. Front. 2017, 4, DOI: 10.1039/c7qo00061h (Invited paper for a themed collection “Novel π-electron molecular scaffolds”)
　　2.Wenting Wu, Hanshen Xin, Congwu Ge, Xike Gao.* Application of direct (hetero)arylation in constructing conjugated small molecules and polymers for organic optoelectronic devices. Tetrahedron. Lett. 2017, 58, 175-184. (Invited Digest paper)
　　3.Yunbin Hu, Zhongli Wang, Xu Zhang, Xiaodi Yang, Congwu Ge, Lina Fu, Xike. Gao.* A Class of Electron-Transporting Vinylogous Tetrathiafulvalenes Constructed by the Dimerization of Core-Expanded Naphthalenediimides. Org. Lett. 2017, 19, 468-471. (Highlighted by Synfacts. 2017, 13, 0373)
　　4.Hanshen Xin, Xike Gao.* Application of Azulene in Constructing Organic Optoelectronic Materials: New Tricks for an Old Dog. ChemPlusChem. 2017, 82, DOI: 10.1002/cplu.201700039 (Invited paper for a special issue on “Novel Aromatics”)
　　5.Hanshen Xin, Congwu Ge, Lina Fu, Xiaodi Yang, Xike Gao.* Naphthalene Diimides Endcapped with Ethynylazulene：Molecular Design, Synthesis and Properties. Chin. J. Org. Chem. 2017, 37, 711-719.
　　6.Hanshen Xin, Congwu\ Ge, Xiaodi Yang, Honglei Gao, Xiaochun Yang, Xike Gao.* Biazulene diimides: a new building block for organic electronic materials. Chem. Sci. 2016, 7, 6701-6705. (Highlighted by Synfacts. 2016, 12, 1040)
　　7.Zheng Zhao, Zhongli Wang, Congwu Ge, Xu Zhang, Xiaodi Yang, Xike Gao* Incorporation of benzothiadiazole into the backbone of 1,2,5,6-naphthalenediimide based copolymers, enabling much improved film crystallinity and charge carrier mobility. Poly. Chem. 2016, 7, 573-579.
　　8.Zheng Zhao, Fengjiao Zhang, Xu Zhang, Simin Gao, Xiaodi Yang,* Zhiming Duan, Xike Gao.* Carbazolo[2,1-a]carbazole Diimide: A Building Block for Organic Electronic Materials. ChemPlusChem. 2015, 80, 57-61. (Early Career Series)
　　9.Bing Leng,* Dong Lu, Xueshun Jia, Xiaodi Yang, Xike Gao.* Synthesis of Monolateraland Bilateral Sulfur-Heterocycle Fused Naphthalene Diimides (NDIs) from Monobromo and Dibromo NDIs. Org. Chem. Front. 2015, 2, 372-377.
　　10.Xike Gao,* Zheng Zhao. High mobility organic semiconductors for field-effect transistors. Sci. China. Chem. 2015, 58, 947-968. (Invited paper for a special issue on “Advances in Organic Optoelectronic Molecules & Materials”)
　　11.Zheng Zhao, Fengjiao Zhang, Yunbin Hu, Zhongli Wang, Bing Leng, Xike Gao,* Chong-an Di, Daoben Zhu. Naphthalene Diimides Fused with 2-(1,3-dithiol-2-ylidene)acetonitrile: Strong Electron-Deficient Building Blocks for High-Performance n-Type Polymeric Semiconductors. ACS Macro Lett. 2014, 3, 1174-1177.
　　12.Yaping Zhang, Fengjiao Zhang, Qing Meng, Chong-an Di,* Xike Gao,* Daoben. Zhu.* Specific and Reproducible Gas Sensors Utilizing Gas-phase Chemical Reaction on Organic Transistors. Adv. Mater. 2014, 26, 2862-2867.
　　13.Xike Gao,* Yunbin Hu. Development of n-Type Organic Semiconductors for Thin Film Transistors: A Viewpoint of Molecular Design. J. Mater. Chem. C, 2014, 2, 3099-3117. (Invited paper for a themed collection: Emerging Investigators)
　　14.Fengjiao Zhang,# Yunbin Hu,# Torben, Schuettfort, Chong-an Di,* Xike Gao,* Christopher R McNeill,* Lars Thomsen, Stefan C B Mannsfeld, Wei Yuan, Henning Sirringhaus, Daoben Zhu.* Critical Role of Alkyl Chain Branching of Organic Semiconductors in Enabling Solution-Processed N-channel Organic Thin-film Transistors with Mobility of up to 3.50 cm2V-1s-1. J. Am. Chem. Soc. 2013, 135, 2338-2349. (# Co-first authors)
　　15.Fengjiao Zhang, Chong-an Di,* Nikolai Berdunov, Yuanyuan Hu, Yunbin Hu, Xike Gao,* Qing Meng, Henning Sirringhaus,* Daoben Zhu.* Ultra-Thin Film Organic Transistors: Precise Control of Semiconductor Thickness via Spin-coating. Adv. Mater. 2013, 25, 1401-1407.
　　16.Zheng Zhao, Fengjiao Zhang, Xu Zhang, Xiaodi Yang, Hongxiang Li, Xike Gao,* Chong-an Di,* Daoben Zhu. 1,2,5,6-Naphthalenediimides-Based Donor-Acceptor Copolymers Designed from Isomer Chemistry for Organic Semiconducting Materials. Macromolecules. 2013, 46, 7705-7714.
　　17.Zheng Zhao, Zhongli Wang, Yunbin Hu, Xiaodi Yang, Hongxiang Li, Xike Gao,* Daoben Zhu. Tetracyanodibenzotetrathiafulvalene Diimides: Design, Synthesis and Property Study. J. Org. Chem. 2013, 78, 12214-12219.
　　18.Yunbin Hu, Zhongli Wang, Xiaodi Yang, Zheng Zhao, Wenjie Han, Wei Yuan, Hongxiang Li, Xike Gao,* Daoben Zhu. A facile synthesis of 2,3,6,7-tetrabromonaphthalene diimides toward new π-extended naphthalene diimides. Tetrahedron Lett. 2013, 54, 2271-2273.
　　19.Yunbin Hu, Zhongli Wang, Xu Zhang, Xiaodi Yang, Hongxiang Li, Xike Gao.* New Core-Expanded Naphthalene Diimides for n-Channel Organic Thin Film Transistors. Chin. J. Chem. 2013, 31, 1428-1438.
　　20.Yunbin Hu, Yunke Qin, Xike Gao,* Fengjiao Zhang, Chong-an Di,* Zheng Zhao, Hongxiang Li, Daoben Zhu.* One-pot synthesis of core-expanded naphthalene diimides: enabling N-substitute modulation for diverse n-type organic materials. Org. Lett. 2012, 14, 292-295.
　　21.Yunbin Hu, Xike Gao,* Chong-an Di,* Xiaodi Yang, Feng Zhang, Yunqi Liu, Hongxiang Li, Daoben Zhu.* Core-expanded naphthalene diimides fused with sulfur heterocycles and end-capped with electron-withdrawing groups for air-stable solution-processed n-channel organic thin film transistors. Chem. Mater. 2011, 23, 1204-1215.
　　22.Yan Zhao, Chong-an Di,* Xike Gao,* Yunbin Hu, Yunlong Guo, Yunqi Liu,* Jizheng Wang, Wenping Hu, Daoben Zhu.* All-Solution-Processed, High-Performance n-Channel Organic Transistors and Circuits: Toward Low-Cost Ambient Electronics Adv. Mater. 2011, 23, 2448-2453.  
　　23.Xike Gao,* Chong-an Di,* Yunbin Hu, Xiaodi Yang, Hongyu Fan, Feng Zhang, Yunqi Liu, Hongxiang Li, Daoben Zhu. Core-expanded naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malonitrile groups for high-performance, ambient-stable, solution-processed n-channel organic thin film transistors. J. Am. Chem. Soc. 2010, 132, 3697-3699.

xinzhou

　立体化学是从三维空间揭示分子的结构、性质、反应行为及功能，手性分子和同分异构体是立体化学的重要研究内容。有机半导体材料是有机光电器件的活性成分，其化学结构和物理化学性质决定着其器件性能和功能应用。目前，有机共轭小分子和聚合物侧链（多为外消旋烷基）的长度和分支点对其半导体性能的影响研究较为广泛，有一定的规律性认识。而立体化学中分子的手性（如中心手性、轴手性、螺旋手性）和构象等对有机半导体材料性能的影响一直未了解清楚，是值得探索的科学问题。
　　中国科学院上海有机化学研究所高希珂课题组致力于新型有机半导体材料的结构创制及功能研究。在前期研究工作中，他们实现了中心手性和轴手性对n-型有机半导体聚集态结构和器件性能的调控（J. Mater. Chem. C, 2019, 7, 2659.; Langmuir 2019, 35, 6188）。近日，他们将立体化学中“阻转异构”的概念应用到有机半导体材料与器件中。研究成果发表在ACS Materials Lett. 2022, 4, 363-369上（highlighted by AZoMaterials as “Atropisomeric Conjugated Diimides in Semiconductors”），高希珂研究员和莫纳什大学Christopher R. McNeill教授为共同通讯作者，上海有机所葛从伍副研究员和张文显为共同第一作者。
　　“阻转异构”（atropisomerism）是由于空间位阻效应使得化合物中化学键的自由旋转受阻而引起的立体化学现象，所形成的可拆分的构象异构体称为“阻转异构体”（atropisomers），例如常见的邻取代联苯。阻转异构已广泛应用于药物化学、超分子化学和有机化学等领域。高希珂课题组设计合成并分离得到了系列室温构象稳定的共轭二酰亚胺类阻转异构体（Syn-NDI, Anti-NDI, Syn-PDI和Anti-PDI，图1），并将其作为有机半导体应用于热刺激-响应型有机场效应晶体管（OFET）器件。研究发现，在热溶液中，这些阻转异构体间均可快速相互转化，而在固态加热条件下，只有Syn-阻转异构体能单向转化为Anti-阻转异构体，反之则不能。Anti-阻转异构体的OFET器件性能受其薄膜热退火温度的影响较小，而Syn-阻转异构体的OFET器件性能受其薄膜热退火温度的影响巨大，这源于热作用下Syn-阻转异构体向Anti-阻转异构体的单向转化。伴随着Syn-NDI转化为Anti-NDI，其OFET器件的电子迁移率提升了近100倍，而Syn-PDI转化为Anti-PDI时，其OFET器件的电子迁移率提升了约5000倍。需要指出的是，热作用下Syn-NDI和Syn-PDI在薄膜中分子构象转化的热退火温度明显不同（图1），这为新型温度传感器的研发提供了研究思路。

图1 阻转异构类有机半导体的化学结构及其热刺激-响应型OFET器件性能

　　该工作得到了国家自然科学基金委、中科院和上海市科委的项目资助