Structure and Photophysical Properties of Silane Bridged Tetraphenylethylene-Oligothiophene Derivatives

doi:10.6023/cjoc202305006

Abstract

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

Cite this article

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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Fig. & Tab. 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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