物理化学学报 >> 2017, Vol. 33 >> Issue (11): 2227-2236.doi: 10.3866/PKU.WHXB201705221

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1, 8-萘酰亚胺衍生物的合成、表征及电存储性能

王漪1,贾南方1,齐胜利1,2,*(),田国峰1,2,武德珍1,2   

  1. 1 北京化工大学,化工资源有效利用国家重点实验室,北京100029
    2 北京化工大学,常州先进材料研究院,江苏常州213164
  • 收稿日期:2017-04-24 发布日期:2017-08-25
  • 通讯作者: 齐胜利 E-mail:qisl@mail.buct.edu.cn
  • 基金资助:
    国家自然科学基金(51673017);国家自然科学基金(21404005);江苏省杰出青年基金(BK20140006);常州市科技计划项目(CZ20150001)

Synthesis, Characterization and Memory Performance of Naphthalimides Containing Various Electron-Withdrawing Moieties

Yi WANG1,Nan-Fang JIA1,Sheng-Li QI1,2,*(),Guo-Feng TIAN1,2,De-Zhen WU1,2   

  1. 1 State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China
    2 Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164, Jiangsu Province, P. R. China
  • Received:2017-04-24 Published:2017-08-25
  • Contact: Sheng-Li QI E-mail:qisl@mail.buct.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(51673017);the National Natural Science Foundation of China(21404005);National Science Fund for Distinguished Young Scholars, China(BK20140006);Changzhou Sci & Tech Program, China(CZ20150001)

摘要:

本文以三苯胺结构作为电子给体,与三种接有不同吸电子基团的1,8-萘酐反应合成了具有电子给-受体结构的N-(4-三苯胺)-1,8-萘酰亚胺(NA-ATPA)、N-(4-三苯胺)-(4-氰基)-1,8-萘酰亚胺(NA(CN)-ATPA)和N-(4-三苯胺)-(4-硝基)-1,8-萘酰亚胺(NA(NO2)-ATPA),并对它们的结构进行了表征。利用紫外可见光谱、荧光发射光谱和循环伏安法对产物的光物理性能和电化学性能进行了测试,并测试了其存储行为,结果显示NA-ATPA表现出易失的静态随机存储行为(SRAM),NACN-ATPA表现出非易失的闪存型存储(Flash),NA(NO2)-ATPA表现出非易失只读型存储(WORM)。三种萘酰亚胺对存储行为中高导态的维持能力逐渐增强,其原因是引入的吸电子基团的吸电子性越强,其LUMO值和能隙值降低的越多,越利于电荷转移,形成更稳定的电荷转移络合物。另外,本文还对原料和产物的电子结构、分子轨道和能级进行了分子模拟计算,研究了三种化合物基态和激发态的差别,并对其电子转移过程进行了理论分析。

关键词: 萘酰亚胺, 吸电子基团, 电荷转移, 分子模拟, 存储性能

Abstract:

In order to clarify the influence of different electron-withdrawing groups on the electronic structures and memory properties of naphthalimides, three 1, 8-naphthalimides, namely N-(4-triphenylamino)-1, 8-naphthalimide (NA-ATPA), N-(4-triphenylamino)-(4-cyano)-1, 8-naphthalimide (NA(CN)-ATPA) and N-(4-triphenylamine)-(4-nitro)-1, 8-naphthalimide (NA(NO2)-ATPA), were designed and synthesized using triphenylamine (TPA) as the electron donor and 1, 8-naphthalene dianhydride containing different electron-withdrawing moieties (-H, -CN, -NO2) as the electron acceptor. The photophysical properties and electrochemical characteristics of the compounds were investigated by ultraviolet-visible spectroscopy (UV-Vis), fluorescence spectroscopy (FL) and cyclic voltammetry (CyV). The synthesized products were applied as the active layer in sandwich devices, whose memory characteristics were tested. NA-ATPA shows volatile static random access memory (SRAM) behavior, while NACN-ATPA and NANO2-ATPA show nonvolatile flash and write-once read-many times memory (WORM) behavior, respectively. Experimental results indicated that the synthesized compounds possessed small energy gaps and wide absorption ranges. The introduction of electron-withdrawing groups on the 4-position of the 1, 8-naphthalimides reduced the LUMO energy level and the energy gap, leading to improved stability of the charge-transfer state and volatile-to-nonvolatile memory transfer. To elucidate the switching mechanism, molecular simulation results, including molecular orbitals, energy levels, optimized geometries, and Mulliken charge populations, were discussed.

Key words: Naphthalimide, Electron-withdrawing group, Charge transfer, Molecular simulation, Storage property

MSC2000: 

  • O641