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%Supramolecular Assembly and Circularly Polarized Luminescence Regulation of a Chiral Dipyrene-Glutamic Acid Amphiphile
河南省科学院同位素研究所有限责任公司 郑州 450015;中国科学院化学研究所 中国科学院胶体、界面与化学热力学重点实验室 北京 100190;河南省科学院质量检验与分析测试研究中心 郑州 450046 中国科学院化学研究所 中国科学院胶体、界面与化学热力学重点实验室 北京 100190
2025-11-01
超分子手性 圆偏振发光 自组装 手性反转 主客体作用
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,glum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.%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,py-rene 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 in-version of ground-state circular dichroism(CD)and excited-state circularly polarized luminescence(CPL)chiral signals.At water fractions of 40%and 90%,the glum values were measured to be-1.31×10-3 and 1.06×10-3,respectively.Upon intro-ducing 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.
