Near-Infrared Aggregation-Induced Emission (AIE) Molecules Based on Coupling of Triarylamine-Modified Benzothiadiazole Units

doi:10.6023/cjoc202407014

Abstract

Three new near-infrared (NIR) aggregation-induced emission (AIE) molecules were constructed by palladium- catalyzed coupling reaction with triarylamine modified benzothiadiazole as a donnor-acceptor (D-A) unit. Their structures were charaterized by ¹H NMR, ¹³C NMR and HRMS. The results of absorption spectroscopic and fluorescence spectroscopic measurements indicated that the absorption maxima of these three compounds in dichloromethean solution were at 525, 521 and 495 nm, respectively, while their emission bands were located at 600~1050 nm. Solvent-dependent spectrosopic studies and theorectical calculations revealed intramolecular charge transfer (ICT) charateristics of these compounds. These compounds exhibited NIR AIE in tetrahydrofuran (THF)/H₂O with emission wavelengths 600~1000 nm and fluorescence quantum yields up to 13%, 10% and 4%, respectively. The results of dynamic light scattering (DLS) and atomic force microscope (AFM) showed that compounds 1~3 formed spherical aggregates of about 80 nm in THF/H₂O (V∶V=8∶2).

Key words: aggregation-induced emission (AIE), near-infrared luminescence, benzothiadiazole, triarylamine

Cite this article

Zixuan Dong, Junjun Su, Hongfei Pan, Xiangkui Ren, Zhijian Chen. Near-Infrared Aggregation-Induced Emission (AIE) Molecules Based on Coupling of Triarylamine-Modified Benzothiadiazole Units[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 205-211.

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Fig. & Tab. 7

Scheme 1. Synthetic route of compounds 1~3

Figure 1. UV-vis absorption spectra of compounds 1~3 in CH2Cl2 (c=1.0×10－5 mol/L)

Figure 2. Fluorescence spectra of compounds 1~3 in CH2Cl2 (c=1.0×10－6 mol/L)

Compd.	λ_max/nm	ε^a/(L•mol^－1•cm^－1)	λ_em^b/nm	Stokes shift/nm	Φ ^c/%	τ/ns	E_g^d/eV	HOMO/eV	LUMO/eV
1	525	56200	791	266	2	3.94	1.59	－5.05	－3.46
2	521	42500	784	263	0.1	3.87	1.60	－5.04	－3.44
3	495	35300	761	266	1	1.19	1.64	－5.03	－3.39

Table 1. Summary of compounds 1~3 characteristic data

Figure 3. Fluorescence spectra of compounds (a) 1, (b) 2 and (c) 3 in different polar solvents (c=1.0×10－6 mol/L, λex=480 nm, all spectra were normalized)

Figure 4. Schematic diagram of the HOMO and LUMO orbitals

Figure 5. Fluorescence spectra of compounds (a) 1, (b) 2 and (c) 3 in THF/H2O, (d) the relationship between fluorescence intensity and water content of compounds 1~3 [Insert: photographs of the solution of compounds 1~3 in THF/H2O (fW=0%, 80%) in cuvettes under UV lamp (365 nm)], and (e) the relationship between fluorescence quantum yield and water content of compounds 1~3 (c=1.0×10－5 mol/L, λex=480 nm)

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