含不同烷基链四苯基丁二烯衍生物的聚集诱导发光及力致变色性能

doi:10.6023/A21120556

摘要/Abstract

设计合成了带有不同长度烷基链、不同极性取代基的四苯基丁二烯(TPB)衍生物TPB-COOCH₃-1~6和TPB-COOH-1~6, 目标化合物均具有显著的聚集诱导发光(AIE)特性及较高的固态荧光量子效率. 烷基链长及取代基极性都会影响目标化合物在聚集时分子排列及分子运动的受限程度, 从而调控其AIE行为. 带有羧酸甲酯的TPB-COOCH₃-1~6中, 丙基取代的TPB-COOCH₃-3在四氢呋喃/水(THF/H₂O)体系中荧光发射增强最为显著; 而羧基取代的TPB-COOH-1~6中, 因亲水性增加, 己基取代的TPB-COOH-6荧光强度增加的倍数最大; 并且, TPB-COOH系列化合物荧光增强的倍数明显低于相同烷基取代的甲酯衍生物TPB-COOCH₃. 此外, 牛血清白蛋白、人血清白蛋白和带有羧基的AIE化合物掺杂时明显影响其固态时的发光及其力致变色性质, 尤其是研磨后会明显提高其荧光强度.

关键词: 聚集诱导发光, 四苯基丁二烯, 烷基链长度, 高荧光量子效率, 力致变色

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

引用此文

张璐璐, 王媛媛, 朱贵楠, 戴文博, 赵紫璇, 赵盈, 支俊格, 董宇平. 含不同烷基链四苯基丁二烯衍生物的聚集诱导发光及力致变色性能[J]. 化学学报, 2022, 80(3): 282-290.

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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图/表 8

图1. 化合物TPB-COOCH3/COOH-1~6的合成路线

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

图2. TPB-COOCH3-3 (a)和TPB-COOH-6 (b)在THF/H2O中的荧光光谱(λex=380 nm; 10-5 mol/L)(插入图为相对荧光强度(I/I0)随φw的变化曲线及其荧光照片, I0和I分别是在纯THF和THF/H2O混合溶液中的荧光强度)

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

表1. TPB-COOCH3-1~6和TPB-COOH-1~6的光物理数据

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

图3. TPB-COOCH3-1~6 (a)和TPB-COOH-1~6 (b)在THF/H2O混合溶液中I/I0随φw的变化趋势(插入图为I/I0的最大值(I/I0,max)及相应水含量随烷基链碳原子个数的变化曲线)

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)

图4. TPB-COOH-4 (a~c) (CCDC 2123962)和TPB-COOH-6 (d~f) (CCDC 2123963)的单晶结构及其分子排列

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

图5. TPB-COOH-2及其与BSA和HSA混合物(即COOH-2+BSA和COOH-2+HSA)的荧光光谱(λex=398 nm; 插入图是相应的I/I0和荧光照片)

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)

图6. TPB-COOH-2, COOH-2+BSA和COOH-2+HSA在研磨前后及用DCM溶解沉淀后样品的相对荧光强度(I/I0)、最大发射波长(λem)及其相应的荧光照片

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

图7. 研磨前后及DCM溶解沉淀后 (a) COOH-2+BSA的红外谱图; (b) TPB-COOH-2, (c) COOH-2+BSA, (d) COOH-2+HSA的PXRD谱图

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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