给体-受体(D-A)型苯基环八四噻吩的合成及其聚集诱导发光与高压发光性能研究

doi:10.6023/cjoc202404001

摘要/Abstract

“马鞍型”环八四噻吩(COTh)是一类有趣的聚集诱导发光(AIE)分子. 通过Suzuki反应, 将强吸电子基团氰基(CN)与强供电子基团甲氧基(OMe)引入到苯环的邻位、间位与对位, 构筑了6种取代苯基的给体-受体(D-A)型Ar-COTh化合物. p-OMe-Ph-COTh的单晶结构分析显示, 分子间存在多重S…C、C…O和O…H相互作用. 这些D-A型Ar-COTh化合物均表现出显著的AIE发光性质, 来源于COTh自身的分子内空间共轭效应(ITSC)所造成的较低能级的激发态发光, 发光峰位与取代基效应关联较小. 其固态发光的荧光量子产率高于AIE态发光. 高压下, 含强吸电子基团的p-CN-Ph-COTh随着压力从0.00 GPa到8.86 GPa的变化, 其荧光发射峰从531 nm红移到了634 nm, 二者相差达103 nm; 而含供电子基团的p-OMe-Ph-COTh随着压力从0.00 GPa到12.0 GPa的变化, 其发射峰只变化了29 nm, 体现出显著的取代基效应与高压发光性质.

关键词: 环八四噻吩(COTh), 给体-受体(D-A)化合物, 合成, 聚集诱导发光(AIE), 高压发光

The saddle-shaped cyclooctatetrathiophene (COTh) is an interesting aggregation induced emission (AIE) molecule. In this work, the strong electron withdrawing group (CN) and the strong electron donating group (OMe) are introduced into the ortho, meta and para positions of benzene ring, reacting with COTh unit through Suzuki reaction to construct six donor-acceptor (D-A) typed substituted phenyl Ar-COTh compounds. The single crystal structure of p-OMe-Ph-COTh shows multiple intermolecular interactions, such as S…C, C…O and O…H interactions among molecules. These D-A typed Ar-COThs exhibit significant AIE luminescence properties, which are mainly attributed to the intramolecular through space conjugation (ITSC) of COTh in excited state. The weak correlation between the emission peak and the substituent effect is observed. The fluorescence quantum yields of Ar-COThs in solid-state luminescence are higher than that of AIE state. Under high pressure, the emission peak of p-CN-Ph-COTh containing strong electron withdrawing group (CN) showed strong bathochromic shift from 531 nm to 634 nm with a big difference of 103 nm under the external pressure change from 0.00 to 8.86 GPa; However, the emission peak of p-OMe-Ph-COTh containing electron donating group (OMe) gave the only change of 29 nm under the pressure change from 0.00 to 12.0 GPa, demonstrating significant substituent and piezochromic effects.

Key words: cyclooctatetrathiophene (COTh), donor-acceptor (D-A) compound, synthesis, aggregation-induced emission (AIE), high pressure luminescence

引用此文

杨玉杰, 曹微, 于际凯, 张志霞, 徐莉, 王华. 给体-受体(D-A)型苯基环八四噻吩的合成及其聚集诱导发光与高压发光性能研究[J]. 有机化学, 2024, 44(8): 2495-2503.

Yujie Yang, Wei Cao, Jikai Yu, Zhixia Zhang, Li Xu, Hua Wang. Synthesis of Donor-Acceptor (D-A) Typed Phenylcyclooctatetrathiophenes and Their Performances on Aggregation Induced Emission and High Pressure Luminescence[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2495-2503.

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图/表 8

图式1. D-A型取代苯基环八四噻吩(Ar-COTh)的合成路线

Scheme 1. Synthetic route to D-A typed Ar-COThs

图1. 化合物p-OMe-Ph-COTh的单晶结构图

Figure 1. Crystal structure of p-OMe-Ph-COTh (A) Molecular structure; (B) unit cell; (C) intermolecular interactions.

化合物	偶极矩^a/D	λ_abs/nm			λ_o_nset/nm	λ_em^AIE/nm	Φ_f^AIE/%	τ/ns	λ_em^Solid/nm	Φ_f^Solid/%
化合物	偶极矩^a/D	Band-І	Band-ІІ	Band-ІІІ	λ_o_nset/nm	λ_em^AIE/nm	Φ_f^AIE/%	τ/ns	λ_em^Solid/nm	Φ_f^Solid/%
Ph-COTh^[11]	0.261	265	298	—	414	522	0.74	5.27	524	4.24
o-OMe-Ph-COTh	2.477	264	287	317	410	522	0.34	7.53	494	3.75
m-OMe-Ph-COTh	1.685	—	290	310	410	522	2.34	6.92	508	3.12
p-OMe-Ph-COTh	2.233	266	—	309	430	526	2.98	2.90	524	9.69
o-CN-Ph-COTh	3.705	—	288	323	420	522	1.36	6.45	507	2.54
m-CN-Ph-COTh	4.851	268	270	311	420	525	0.71	6.45	493	1.99
p-CN-Ph-COTh	5.479	—	273	324	425	529	1.03	6.52	526	2.47

表1. D-A型取代苯基环八四噻吩的光物理数据

Table 1. Photophysical data of D-A typed Ar-COThs

图2. 化合物Ar-COThs在四氢呋喃中的紫外-可见吸收光谱 (c=1×10－5 mol/L)

Figure 2. UV-vis absorption spectra of Ar-COThs in THF (c=1×10－5 mol/L)

图3. o-OMe-Ph-COTh在THF-H2O二元体系中的(A)荧光光谱(λex=330 nm, c=1×10－5 mol/L), 以及(B) 523 nm处的荧光强度与水含量的关系图和样品照片(插图, 在365 nm紫外灯照射下拍摄)

Figure 3. (A) PL spectra of o-OMe-Ph-COTh in THF/water mixtures (c=1×10－5 mol/L, λex=330 nm), (B) changes of PL peak intensities at 523 nm vs the water fraction in the THF/water mixtures and PL photos of the sample (inset: the photos were taken under the 365 nm UV light)

图4. p-CN-Ph-COTh在THF-H2O二元体系中的(A)荧光光谱(λex=320 nm, c=1×10－5 mol/L), 以及(B) 522 nm处的荧光强度与水含量的关系图和样品照片(插图: 365 nm紫外灯照射下拍摄)

Figure 4. (A) PL spectra of p-CN-Ph-COTh in THF/water mixtures (c=1×10－5 mol/L, λex=320 nm), (B) changes of PL peak intensities at 522 nm vs the water fraction in the THF/water mixtures, and PL photos of the sample (inset: the photos were taken under the 365 nm UV light)

图5. (A) p-CN-Ph-COTh的高压发光光谱、(B)发光峰位-压力关系图、(C) 355 nm激发下发光照片、 (D)白光下的样品颜色照片

Figure 5. (A) PL photos of p-CN-Ph-COTh under different high pressures, (B) plot of emission intensity versus the hydrostatic pressure, (C) corresponding PL photographs excited by a 355 nm laser, and (D) corresponding photographs of sample color under white light

图6. (A) p-OMe-Ph-COTh高压发光光谱、(B)发光峰位-压力关系图、(C) 355 nm激发下发光照片、(D)白光下的样品颜色照片

Figure 6. (A) PL photos of p-OMe-Ph-COTh under different high pressures, (B) plot of emission intensity versus the hydrostatic pressure, (C) corresponding PL photographs excited by a 355 nm laser, and (D) corresponding photographs of sample color under white light

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