Aggregation-Induced Emission and Mechanochromism of the Tetraphenylbutadiene Derivatives Containing Different Alkyl Chains

doi:10.6023/A21120556

Abstract

Series of 1,1,4,4-tetraphenylbuta-1,3-diene (TPB) derivatives, named TPB-COOCH₃-1~6 and TPB-COOH-1~6 containing different alkyl chains and polar substituents, were designed and synthesized by terminal alkyne dimerization and Pd-catalyzed cross-coupling, etc. The target compounds were characterized by ¹H nuclear magnetic resonance, ¹³C nuclear magnetic resonance, mass spectrum, Fourier transform infrared, from which satisfactory results to their molecular structures were obtained. They all have good thermal stabilities with high decomposition temperatures above 310 ℃ based on thermogravimetric analysis. Investigation of the photophysical properties indicated that the target compounds exhibited significant aggregation-induced emission (AIE) features with higher α_AIE (α_AIE=Φ_PL,solid/Φ_PL,solu) values of 20.5~49.6 for TPB-COOCH₃-1~6 and 14.4~26.3 for TPB-COOH-1~6, and their photoluminescence quantum yields in solid state (Φ_PL,solid) were determined as high as 71.3%~89.1% and 34.5%~73.2% for TPB-COOCH₃-1~6 and TPB-COOH-1~6, respectively. The different lengths of alkyl chains and the polarity of the other substituent had obvious effect on the regular molecular stacking of the target compounds when they were forced to aggregate or precipitate, which affects the intermolecular interaction and the restriction degree of the rotators, consequently influenced their AIE behavior in the tetrahydrofuran (THF)/H₂O mixtures. For the compounds TPB-COOCH₃-1~6 containing methyl esters and different alkyl chains, TPB-COOCH₃-3, which is with n-propyl, exhibited the most significant fluorescence enhancement (I/I₀=26.0) in the THF/H₂O mixtures. While, for TPB-COOH-1~6 containing -COOH and alkyl chains, TPB-COOH-6, which is with n-hexyl, had the maximum I/I₀ (I/I₀=15.7) due to the increase of hydrophilicity. Careful comparison revealed that the I/I₀ and Φ_PL,solidvalues of TPB-COOCH₃-1~6 were higher than those of TPB-COOH-1~6 containing same alkyl chains under the same measuring condition, mainly attributing to the interaction between the -COOH groups or between -COOH and the polar solvent molecules, which increasing the nonradiative energy decay and weakening fluorescence emission. Furthermore, the incorporation of bovine serum albumin (BSA) and human serum albumin (HSA) into TPB-COOH significantly enhanced the solid-state fluorescence emission, and the BSA and HSA also influenced the mechanochromic properties of the AIEgens containing -COOH. Especially, the fluorescence intensity increased obviously after grinding the doped system of TPB-COOH-2 and BSA, mainly because the existence and steric hindrance of BSA molecules weakened the π-π interaction of the planarized TPB-COOH-2 molecules, which effectively inhibiting the intramolecular rotation of benzene ring and reducing the nonradia tive energy loss.

Key words: aggregation-induced emission, tetraphenylbutadiene, alkyl chains, high fluorescence quantum yield, mechanochromism

Cite this article

Lulu Zhang, Yuanyuan Wang, Guinan Zhu, Wenbo Dai, Zixuan Zhao, Ying Zhao, Junge Zhi, Yuping Dong. Aggregation-Induced Emission and Mechanochromism of the Tetraphenylbutadiene Derivatives Containing Different Alkyl Chains[J]. Acta Chimica Sinica, 2022, 80(3): 282-290.

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Fig. & Tab. 8

Figure 1. The synthetic route of TPB-COOCH3/COOH-1~6

Figure 2. Fluorescence spectra of TPB-COOCH3-3 (a) and TPB-COOH-6 (b) in THF/H2O mixtures (λex=380 nm; 10-5 mol/L) (The inserts are the plot of I/I0 vs. φw and their fluorescence images, I0 and I are the PL intensities in pure THF and THF/H2O mixtures, respectively)

样品	溶液^a							固体				α_AIE^d
样品	λ_abs/nm		λ_em/nm	Δλ^b/nm	Δν_st^b/cm^-1	Φ_PL^c/%	I/I₀	λ_em/nm		Φ_PL^c/%		α_AIE^d
TPB-COOCH₃-1		368	470	102	5934	3.7	12.8	462		76.5		20.5
TPB-COOCH₃-2		368	470	102	5934	3.8	18.5	460		80.1		20.6
TPB-COOCH₃-3		370	472	102	5840	1.8	26.0	472		87.3		49.6
TPB-COOCH₃-4		373	471	98	5614	1. 9	22.9	470		89.1		47.1
TPB-COOCH₃-5		370	471	101	5796	2.1	19.3	470		87.5		41.9
TPB-COOCH₃-6		370	471	101	5796	2.2	19.0	470		71.3		32.4
TPB-COOH-1		365	471	106	6166	3.9	11.3	496		55.6	14.4
TPB-COOH-2		365	470	105	6120	2.4	8.2	480		34.5	14.5
TPB-COOH-3		368	471	103	5979	2.1	11.6	500		42.8	20.8
TPB-COOH-4		368	472	104	6024	2.4	12.9	490		52.3	22.2
TPB-COOH-5		368	475	107	6158	2.3	14.9		492	60.9	26.3
TPB-COOH-6		368	475	107	6158	3.0	15.7		493	73.2	24.7

Table 1. The photophysical date of TPB-COOCH3-1~6 and TPB-COOH-1~6

Figure 3. The curves of I/I0 vs. φw in THF/H2O mixtures for TPB-COOCH3-1~6 (a) and TPB-COOH-1~6 (b) (The inserts are the plots of the maximum I/I0 values (I/I0,max) and the corresponding φw changing with the number of carbon atom in the alkyl groups)

Figure 4. The crystal structures, molecular packing patterns of TPB-COOH-4 (a~c) (CCDC 2123962) and TPB-COOH-6 (d~f) (CCDC 2123963)

Figure 5. Fluorescence spectra of TPB-COOH-2, COOH-2+BSA and COOH-2+HSA (λex=398 nm; the inserts are the corresponding I/I0 and fluorescence images)

Figure 6. The I/I0, λem of the pristine, ground and returned solid samples of TPB-COOH-2, COOH-2+BSA, COOH-2+HSA, and their fluorescence images

Figure 7. IR spectra of (a) COOH-2+BSA; and PXRD patterns of (b) TPB-COOH-2, (c) COOH-2+BSA, (d) COOH-2+HSA in their pristine, ground and returned states

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