酰亚胺稠合萘并[2，3-b：6，7-b′]二呋喃衍生物的合成与性质

Synthesis and Properties of Imide-fused Naphtho［2，3-b：6，7-b′］difuran Derivatives

摘要

稠合呋喃及其衍生物具有高刚性、良好的共面性及扩展的π-共轭结构，已被用于发展有机光电功能材料.然而，与稠合噻吩及其衍生物相比，稠合呋喃及其衍生物的结构种类仍然有限，制约了其进一步发展.基于此，本文将酰亚胺基团与萘并[2，3-b∶6，7-b']二呋喃(NDF)单元稠合，合成了DFPI-Cn系列分子，研究了分子的理化性质及其在有机场效应晶体管器件中的性能.结果表明，所有分子均表现出良好的热稳定性，且随着烷基侧链增长，其结晶温度与熔融温度逐渐降低.分子骨架呈轻微扭曲，最高占据分子轨道与最低未占据分子轨道的电子云均匀分布于整个共轭骨架中.酰亚胺N位烷基链对分子在溶液中的吸收与发射光谱无明显影响，但对固体薄膜中的吸收光谱具有显著调控作用.3个分子均呈现红光发射.单晶结构解析表明，DFPI-C5C5分子采取一维堆积方式：相邻两个分子以头对尾方式形成二聚体，二聚体之间再以一定旋转角进行堆叠.采用物理气相传输法制备的DFPI-C5C5纳米线晶体具有单晶特性及平整的表面形貌.基于该纳米线晶体构建的有机场效应晶体管器件展现p型电荷传输特性，空穴迁移率达3.7×10^-3 cm²·V^-1·s^-1.本研究为发展新型稠合呋喃类有机半导体材料提供了新思路.

Abstract

Fused furans and their derivatives have been used to develop organic optoelectronic functional materials due to their high rigidity，good coplanarity，and extended π-conjugated structure.However，compared with fused thiophenes and their derivatives，the structural diversity of fused furans and their derivatives remains limited，which restricts their further development.To address this issue，we fused imide groups with naphtha［2，3-b∶6，7-b'］difuran（NDF）units to synthesize a series of DFPI-Cn molecules，and systematically investigated their physicochemical properties as well as their performance in organic field-effect transistor devices.All the molecules exhibit good thermal stability，and their crystallization and melting temperatures gradually decrease with increasing alkyl side chain length.The molecular skeleton is slightly twisted，and the electron cloud distributions of the highest occupied molecular orbital and the lowest unoccupied molecular orbital are uniformly delocalized over the entire conjugated framework.The N-alkyl chains of the imide groups have no obvious effect on the absorption and emission spectra of the molecules in solution，but significantly modulate their absorption spectra in solid films.All three molecules show red emission.Single-crystal structure analysis reveals that DFPI-C5C5 molecules adopt a one-dimensional packing mode：two adjacent molecules form a dimer in a head-to-tail manner，and the dimers further stack with a certain rotation angle.The DFPI-C5C5 nanowire crystals prepared by physical vapor transport exhibit single-crystal characteristics and a flat surface morphology.Organic field-effect transistor devices based on these nanowire crystals show p-type charge transport properties with a hole mobility of up to 3.7×10^-3 cm²·V^-1·s^-1.This work provides a new approach for the development of novel fused furan-based organic semiconductor materials.

关键词

稠合呋喃 / 共轭分子 / 酰亚胺

Key words

Fused furan / Conjugated molecule / Imide

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基金资助

天津市自然科学基金(23JCYBJC01790)