手性双芘-谷氨酸两亲分子的超分子组装及圆偏振发光调控

doi:10.6023/cjoc202505001

摘要/Abstract

以手性双芘-谷氨酸两亲分子(PyG)为研究对象, 通过反溶剂和主客体相互作用调控其超分子组装行为, 实现了圆偏振发光(CPL)增强与手性反转. 研究发现, 在N,N-二甲基甲酰胺(DMF)/H₂O混合溶剂中, 不良溶剂水含量的变化可调控PyG芘基团堆积模式. 水含量较高时芘发色团以单体发射为主, 而水含量较低时主要为激基缔合物(excimer)发射, 同时芘基团重叠方式的差异显著影响组装体的手性光学性质, 实现了基态圆二色(CD)与激发态圆偏振发光(CPL)手性信号的反转(特征水比例40%和90%下, g_lum值分别为－1.31×10^－3和1.06×10^－3). 当进一步往体系中加入β-环糊精(β-CD)时, β-CD可与PyG形成1∶1的络合物, β-CD的分子手性可以控制共组装体的超分子手性, 此时L-Py/β-CD和D-PyG/β-CD均给出负的CPL信号.

关键词: 超分子手性, 圆偏振发光, 自组装, 手性反转, 主客体作用

This study focuses on the chiral bipyrene-glutamic acid amphiphilic molecule (PyG), regulating its supramolecular assembly behavior through anti-solvent and host-guest interactions to achieve enhanced circularly polarized luminescence (CPL) and chirality inversion. Our work reveals that in N,N-dimethylformamide (DMF)/H₂O mixed solvents, variations in water content (poor solvent) can modulate the stacking patterns of pyrene chromophores in PyG. At higher water content, pyrene chromophores predominantly exhibit monomer emission, while lower water content favors excimer emission. The distinct overlap modes of pyrene groups significantly influence the chiral optical properties of assemblies, enabling simultaneous inversion of ground-state circular dichroism (CD) and excited-state circularly polarized luminescence (CPL) chiral signals. At water fractions of 40% and 90%, the g_lum values were measured to be －1.31×10^－3 and 1.06×10^－3, respectively. Upon introducing β-cyclodextrin (β-CD) into the system, a 1∶1 complex forms between β-CD and PyG. The molecular chirality of β-CD governs the supramolecular chirality of co-assemblies with both L-PyG/β-CD and D-PyG/β-CD systems displaying negative CPL signals.

Key words: supramolecular chirality, circularly polarized luminescence, self-assembly, chirality inversion, host-guest interactions

引用此文

赵晨阳, 任静晓, 欧阳光辉, 刘鸣华. 手性双芘-谷氨酸两亲分子的超分子组装及圆偏振发光调控[J]. 有机化学, 2025, 45(11): 4171-4177.

Chenyang Zhao, Jingxiao Ren, Guanghui Ouyang, Minghua Liu. Supramolecular Assembly and Circularly Polarized Luminescence Regulation of a Chiral Dipyrene-Glutamic Acid Amphiphile[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4171-4177.

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图/表 4

图1. (a) L-PyG的分子结构式; (b) L-PyG在不同溶剂中的UV-vis光谱; (c) L-PyG在不同溶剂中的FL光谱(插图为PyG溶液在365 nm紫外灯下的照片, 从左至右依次为1,4-二氧六环, DMF和MeOH); (d) D-PyG的分子结构式; (e) L-PyG在不同溶剂中的CD光谱; (f) L-PyG在不同溶剂中的CPL光谱

Figure 1. (a) Molecular structure of L-PyG; (b) UV-vis spectra of L-PyG in different solvents; (c) FL spectra of L-PyG in different solvents (The inserted images are photographs of PyG in different solution, from left to right: 1,4-dioxane, DMF, MeOH); (d) Molecular structure of D-PyG; (e) CD spectra of L-PyG in different solvents; (f) CPL spectra of L-PyG in different solvents For all measurements, the concentration of PyG was 1.3×10－⁴ mol/L, the cuvette path length was 2 mm, excitation wavelengths for fluorescence and CPL spectra were 340 and 320 nm, respectively.

图2. (a) fw从10%到90%的L-PyG组装体的荧光光谱图; (b) fw从10%到90%的L-PyG组装体的CD光谱图; (c) L-PyG(实线)和D-PyG(虚线)组装体在水含量为40%和90%时的CD光谱图; (d) L-PyG组装体fw由10%升高到90%的CPL光谱图; (e) fw=40%的L-PyG组装体扫描电镜图; (f) fw=90%的L-PyG组装体扫描电镜图

Figure 2. (a) Fluorescence spectra of L-PyG assemblies with fw ranging from 10% to 90%; (b) CD spectra of L-PyG assemblies with fw ranging from 10% to 90%; (c) CD spectra of L-PyG assemblies and D-PyG assemblies at fw=90% and 40%; (d) CPL spectra of L-PyG assemblies with fw ranging from 10% to 90%; (e) SEM image of L-PyG assemblies at fw=40%; (f) SEM image of L-PyG assemblies at fw=90% [PyG]=3.9×10－3 mol/L, cuvette path length 0.1 mm, λex=340 nm and 320 nm for FL and CPL measurements. The blue, red, and black lines represent systems with fw=90%, 40%, and 10%, respectively, while the gray dashed lines correspond to other water fractions.

图3. (a) fw=90%(蓝线)和fw=40%(红线)时组装体的PXRD图; (b) fw=90%(蓝线)和fw=40%(红线)时组装体的FT-IR图([PyG]=3.9×10－3 mol/L, DMF/H2O混合溶剂); (c)水含量调控的芘发色团堆积与CPL反转机理图

Figure 3. (a) PXRD patterns of the assemblies at fw=90% (blue line) and fw=40% (red line); (b) FT-IR spectra of the assemblies at fw=90% (blue line) and fw=40% (red line) ([PyG]=3.9×10－3 mol/L in DMF/H2O co-solvents); (c) Schematic ilustration of CPL inversion through water-dependent pyrene stacking

图4. (a) 298 K下PyG的锂盐与β-CD (0~4 equiv.)的UV-vis光谱([PyG]=5.23×10－5 mol/L, 比色皿光程1 cm); (b)基于图4a的1∶1非线性拟合曲线; (c) Benesi-Hildebrand方程显示1∶1结合模式(结合常数Ka=7.87×103 L•mol－1); (d) PyG的锂盐与β-CD的紫外可见光谱滴定的Job曲线([PyG]＋[β-CD]=5.23×10－5 mol/L); (e) L-PyG和β-CD (0, 1, 2, 10 equiv.)共组装的CPL光谱(插图: 加入不同物质的量β-CD的样品瓶在365 nm紫外灯下的照片, 从左至右β-CD的用量依次为0, 1, 2, 10 equiv.); (f) D-PyG和不同物质的量的β-CD共组装的CPL光谱([PyG]=2.6×10－4 mol/L, 比色皿光程为1 cm)

Figure 4. (a) UV-vis spectra of PyG lithium salt with gradually added β-CD (0~4 equiv.) at 298 K ([PyG]=5.23×10⁻⁵ mol/L, cuvette path length=1 cm); (b) Nonlinear fitting curve for a 1∶1 binding model based on the data in Figure 4a; (c) Benesi-Hildebrand plot confirming a 1∶1 binding stoichiometry (binding constant Ka=7.87×103 L•mol－1); (d) Job’s plot for the UV-vis titration of PyG lithium salt with β-CD ([PyG]＋[β-CD]=5.23×10⁻5 mol/L); (e) CPL spectra of L-PyG co-assembled with varying equiv. of β-CD (0, 1, 2, 10 equiv.) (Inset: photographs of samples under 365 nm UV light, from left to right: 0, 1, 2, 10 equiv. β-CD); (f) CPL spectra of D-PyG co-assembled with varying equiv. of β-CD ([PyG]=2.6×10⁻⁴ mol/L, cuvette path length=1 cm)

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