新型茚并芴-5,7-二酮衍生物的合成与性质研究

doi:10.6023/cjoc202412016

摘要/Abstract

设计并合成了不同烷基链修饰的茚并芴-5,7-二酮衍生物, 烷基链的引入不但提高了分子的溶解性, 使分子便于分离提纯和结构表征, 而且可以调控分子的性质来进一步探讨分子结构与性质的关系. 性质研究发现新化合物的溶解性好, 热学和光学稳定性高. 化合物5b~5d的最低空分子轨道(LUMO)能级均低于－3.4 eV, 说明它们具有较高的电子亲和能. 3,9-二叔丁基茚并芴-5,7-二酮(5d)的单晶结构显示其形成了近似平面的五元环骨架和面对面的层状堆积, 层间距为0.3541 nm, 羰基在相邻堆积层中的方向相反. 分子层之间较强的π-π相互作用有利于载流子的传输, 为有机功能分子的设计提供了一定的指导, 同时为有机场效应晶体管的研究提供新的材料来源.

关键词: 茚并芴-5,7-二酮, 有机功能材料, Suzuki偶联反应

Indeno[2,1-b]fluorene-5,7-dione derivatives modified by different alkyl chains were designed and synthesized. The introduced alkyl chains not only improved the solubility of the compounds, which facilitated the separation and purification to characterize their structures, but also regulated the properties and then proved the chance to investigate the relationship between the structure and property. It was found that the solubility, thermal and optical stability of the new compounds were good. Compounds 5b~5d have increased electronegativities because of the lowest unoccupied molecular orbital (LUMO) energies (≤－3.4 eV). The crystalline structure of 3,9-ditert-butylindeno]2,1-b]fluorene-5,7-dione (5d) shows that it forms a nearly planar five-membered ring skeleton and slipped face-to-face π-stacks with a layer space of 0.3541 nm, and the direction of carbonyl groups in adjacent deposits is opposite. The molecular packing could facilitate carrier transport. This article provides some guidance for the design of organic functional molecules, and provides new materials source for field effect transistors.

Key words: indeno[2,1-b]fluorine-5,7-dione, organic functional material, Suzuki coupling reaction

引用此文

王静, 陈宇讯, 姜静静. 新型茚并芴-5,7-二酮衍生物的合成与性质研究[J]. 有机化学, 2025, 45(7): 2444-2450.

Jing Wang, Yuxun Chen, Jingjing Jiang. Study on Synthesis and Properties of New Indeno[2,1-b]fluorene-5,7-dione Derivatives[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2444-2450.

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图/表 8

图式1. 化合物5a~5d的合成路线

Scheme 1. Synthetic route to compounds 5a~5d

图1. 5a~5d (10 μmol/L)在二氯甲烷溶剂中的归一化紫外-可见吸收光谱

Figure 1. Normalized UV-vis absorption spectra in DCM of 5a~5d (10 μmol/L)

Compd.	λ_abs/nm	E_g^a/eV	λ_em/nm	T_dec/℃	E1 red/V	E2 red/V	E3 red/V	Eonset red/V	E_HOMO^b/eV	E_LUMO^c/eV
5a	440, 405, 385, 320, 305, 282	2.61	544	418
5b	485, 450, 413, 390, 338, 325, 282	2.43	557	413	－1.32	－1.64	—	－0.97	－5.86	－3.43
5c	485, 450, 413, 390, 338, 325, 282	2.42	558	416	－1.23	－1.55	－1.74	－0.92	－5.90	－3.48
5d	485, 450, 410, 389, 338, 325, 282	2.43	556	420	－1.08	－1.45	－1.65	－0.91	－5.92	－3.49

表1. 化合物5a~5d的光学、热分解温度和电化学数据

Table 1. Optical data, decomposition temperatures and electrochemical properties for compounds 5a~5d

图2. 5a~5d在18 ℃和自然光照条件下的紫外吸收减小及其光稳定性

Figure 2. Photo-stability of 5a~5d monitored through decrease in their absorption upon exposure to ambient light and air at 18 ℃

图3. 5a~5d (10 μmol/L)在二氯甲烷溶剂中的归一化荧光光谱

Figure 3. Normalized fluorescence spectra of 5a~5d (10 μmol/L) recorded in DCM Excitation wavelength of 5a~5d: 350 nm, slit width 5 nm.

图4. 5b~5d (0.001 mol/L)的循环伏安曲线图

Figure 4. Cyclic voltammograms of 5b~5d (0.001 mol/L)

图5. 5a~5d在氮气保护下升温速度为10 ℃•min－1时的TGA曲线

Figure 5. TGA plots of 5a~5d with a heating rate of 10 ℃• min－1 under N2

图6. 5d的单晶结构

Figure 6. X-ray crystal structure of 5d Red spheres depict O atoms and gray spheres represent C; Hydrogen atoms have been omitted for clarity in packing.

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