硅烷桥联四苯乙烯-寡聚噻吩衍生物的结构与光谱性质

doi:10.6023/cjoc202305006

摘要/Abstract

设计合成了一系列硅烷桥联四苯乙烯(TPE)-寡聚噻吩衍生物. 硅烷取代基为甲基和苯基, 寡聚噻吩单元中噻吩数量为1~3, 通过空间位阻效应和电子效应调控分子的固态发光性质. 具有苯基取代基的硅烷和二噻吩分子表现出高达64.5%的固态发光. 含1或2个噻吩单元的分子的固态和液态荧光性质类似四苯乙烯, 而含3个噻吩的分子的发光则主要来自于三噻吩, 其在液态和聚集态分别有1.4%和14%的发光效率. 苯基硅烷桥联三噻吩-四苯乙烯分子的聚集体具有检测硝基爆炸物的能力和防伪应用潜力.

关键词: 硅烷, 四苯乙烯, 寡聚硅烷, 荧光

A series of silane-bridged tetraphenylethene (TPE)-oligothiophene derivatives were synthesized. The silane substituents varied from methyl to phenyl groups, while the number of thiophene units in the oligothiophene segment was 1 to 3. The solid-state luminescence properties of the molecules were regulated by steric hindrance and electronic effects. Phenyl substituted silane-bridged bithiophene (BT)-TPE molecules exhibited up to 64.5% solid-state luminescence. Molecules containing 1 or 2 thiophene units exhibited fluorescence properties similar to TPE in both solid and liquid states, while the emission of molecules containing 3 thiophene units mainly came from terthiophene (TT) with luminescence efficiencies of 1.4% and 14% in liquid and aggregated states, respectively. The aggregate of phenyl substituted silane-bridged TT-TPE molecules exhibited potential for detecting nitro explosives and anti-counterfeiting applications.

Key words: silane, tetraphenylethene, oligothiophene, luminescence

引用此文

余富欢, 周志宽, 谢威, 周传庭, 盖立志, 卢华. 硅烷桥联四苯乙烯-寡聚噻吩衍生物的结构与光谱性质[J]. 有机化学, 2023, 43(10): 3652-3660.

Fuhuan Yu, Zhikuan Zhou, Wei Xie, Chuanting Zhou, Lizhi Gai, Hua Lu. Structure and Photophysical Properties of Silane Bridged Tetraphenylethylene-Oligothiophene Derivatives[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3652-3660.

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图/表 9

Scheme 1. Synthetic routes and chemical structures of 3~6b

Figure 1. UV absorption spectra of compounds 3~6, TPE, BT, and TT in THF.

Figure 2. (a) Photographs of compounds 3~6 before and after UV irradiation in THF solution and powder form, and fluorescence spectra of compounds 3~6 in (b) THF solution and (c) solid powders

Compd.	λ_abs/nm	THF		95% H₂O/THF		Powder
Compd.	λ_abs/nm	λ_em/nm	QY^a/%	λ_em/nm	QY^a/%	λ_em/nm	QY^a/%
3	313	376	0.5	468	26.7	450	12.6
4	313	376	0.4	471	21.2	475	13.5
5a	320	383	0.4	469	21.2	463	17.4
5b	323	385	0.5	469	31.6	526	64.5
6a	326, 363	423, 446	1.4	465, 495	7.2	467	10.3
6b	326, 370	427, 450	1.4	521, 556	23.9	512	14.0

Table 1. Absorption and fluorescence data of compounds 3~6b in THF, 95% H2O/THF, and powder forms.

Figure 3. Emission spectra of compounds (a) 3, (b) 4, (c) 5a, (d) 5b, (e) 6a and (f) 6b in various THF/water mixtures Inserts show the photographs of compounds in mixed solvents under 365 nm UV irradiation. fw: the proportion of water in the total solvent volume (fw=Vwater/(VTHF＋Vwater), where V is volume.

Figure 4. Single crystal structures and crystal packings of (a) 5a (CCDC 2252772) and (b) 6a (CCDC 2252773)

Figure 5. HOMOs and LUMOs of 3~6b calculated with B3LYP/6-31G(d) level

Figure 6. Fluorescence titration spectra of compound 6b with various equivalents of (a) nitrobenzene and (b) 4-nitrotoluene in THF/water mixtures where fw=95%

Figure 7. Fluorescence photographs of the letters “HZNU” written on filter papers using ink containing TPE (top line) and 6b (bottom line) under different conditions

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