萘二酰亚胺同分异构体化合物的设计合成及其单分子导电性能研究  

Design, synthesis and single-molecular conductivity of isomeric naphthalene diimides

作　　者：彭培珍 白杰 李建高 黄金涛 吴文婷 洪文晶 高希珂[1] Peizhen Peng;Jie Bai;Jiangao Li;Jintao Huang;Wenting Wu;Wenjing Hong;Xike Gao(Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China;College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

机构地区：[1]中国科学院上海有机化学研究所,中国科学院有机功能分子合成与组装化学重点实验室,上海200032 [2]厦门大学化学化工学院,厦门361005

出　　处：《中国科学：化学》2022年第2期339-346,共8页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(21674126,21790362);中科院战略性先导B项目(XDB12010100);上海市科委项目(18JC1410600,19XD1424700)资助。

摘　　要：本文设计合成了两个4-甲硫基苯乙炔基取代的1,4,5,8-萘二酰亚胺(1,4,5,8-NDI)和1,2,5,6-萘二酰亚胺(1,2,5,6-NDI)同分异构体化合物1和2,并用紫外-可见吸收光谱、电化学等手段研究了其物理化学性质.化合物1和2结构上的差异导致其物理化学性质以及单分子器件性能表现出差异.密度泛函理论(DFT)计算表明,基于1,4,5,8-NDI的化合物1具有更低的最高已占轨道(HOMO)/最低未占轨道(LUMO)能级,更有利于电子的传输.利用扫描隧道显微镜裂结技术(STM-BJ)技术制备了化合物1和2的单分子结,并研究了其导电行为.在离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIPF_(6))中施加0.1 V电位,化合物1和2的电导值分别为10^(−3.70)G_(0)(15.5 nS,1G_(0)=77.5μS)和10^(−3.90)G_(0)(9.8 nS),表明化合物1具有更好的导电能力.Two isomeric 4-methylthiophenylethynyl-substituted 1,4,5,8-naphthalene diimide(1,4,5,8-NDI)and 1,2,5,6-naphthalene diimide(1,2,5,6-NDI)derivatives 1 and 2 were designed and synthesized.The physicochemical properties of 1 and 2 were studied by means of ultraviolet-visible(UV-vis)spectra,electrochemical measurements and density functional theory(DFT)calculations.The structural differences between 1 and 2 led to their different physicochemical properties and single-molecule device performance.Compound 1 based on 1,4,5,8-NDI that has lower highest occupied molecular orbital(HOMO)/lowest unoccupied molecular orbital(LUMO)energy levels and narrower band gap is more conducive to electron transport relative to compound 2 with 1,2,5,6-NDI core.The single-molecular junctions of 1 and 2 were prepared by scanning tunneling microscope-break junctions(STM-BJ)technique,and their conductive behaviors were studied.When the potential of 0.1 V was applied in the ionic liquid BMIPF_(6),the conductance of single-molecular junctions of 1 and 2 was 10^(−3.70) G_(0)(15.5 nS,1G_(0)=77.5μS)and 10^(−3.90) G_(0)(9.8 nS),respectively,and the single-molecule device based on 1 has a better conductivity.

关 键 词：萘二酰亚胺 结构异构 单分子器件 

分 类 号：TQ246.31[化学工程—有机化工] TN03[电子电信—物理电子学]