Synthesis of Donor-Acceptor (D-A) Typed Phenylcyclooctatetrathiophenes and Their Performances on Aggregation Induced Emission and High Pressure Luminescence

doi:10.6023/cjoc202404001

Abstract

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

Cite this article

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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Fig. & Tab. 8

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

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

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

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

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)

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)

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

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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