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Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited‐State “Majority Rule” in Enantiomeric Dansulfonamide Assemblies
Small ( IF 13.3 ) Pub Date : 2024-05-11 , DOI: 10.1002/smll.202401954
Xin Wen 1, 2 , Fulin Wang 1 , Sifan Du 1 , Yuqian Jiang 3 , Li Zhang 1 , Minghua Liu 1, 2
Affiliation  

Achiral solvents are commonly utilized to induce the self‐assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited‐state “majority rule” in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self‐assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of “mixed enantiomers”. The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited‐state chiroptical properties.

中文翻译:

对映体丹磺酰胺组装中的非手性溶剂反螺旋路径和共溶剂控制的激发态“多数法则”

非手性溶剂通常用于诱导手性分子的自组装。这项研究表明,非手性溶剂可以触发丹磺酰两亲物组装体中的螺旋性反转,并通过改变共溶剂比例来控制由纯对映体组成的组装体中的激发态“多数法则”。具体来说,丹磺酰两亲物的对映体在甲醇(MeOH)和乙腈(MeCN)中自组装成具有相反旋向的螺旋结构,并具有反圆二色性和圆偏振发光(CPL)信号。当使用 MeOH 和 MeCN 的混合物时,非手性共溶剂以类似于“混合对映体”的方式共同影响组件的 CPL。主要共溶剂控制 CPL 信号。随着共溶剂成分从纯 MeCN 转变为 MeOH,CPL 信号经历显着的反转和放大,在 ≈20% MeOH 和 20% MeCN 处观察到两个最大值。这项研究加深了对非手性溶剂如何调节螺旋纳米结构及其激发态手性光学性质的理解。
更新日期:2024-05-11
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