Although F‐containing molecules and macromolecules are often used in molecular biology to increase the binding with Lewis acidic groups by introducing favorable C‐F dipoles, there is virtually no experimental evidence and limited understanding of the nature of these interactions, especially their role in synthetic polymeric materials. These studies elucidate the molecular origin of inter‐ and intra‐chain interactions responsible for self‐healing of F‐containing copolymers composed of pentafluorostyrene and n‐butyl acrylate units (p(PFS/nBA). Guided by dynamic surface oscillating force (SOF) and spectroscopic measurements supported by molecular dynamics (MD) simulations, these studies show that the reformation of σ‐σ orbitals in ‐C‐F of PFS and CH3CH2‐ of nBA units enables the recovery of entropic energy via flouorophilic‐σ‐lock van der Waals forces when PFS/nBA molar ratios are ~50/50. The strength of these interactions determined experimentally for self‐healable PFS/nBA compositions is in the order ~0.3 kcal/mol which primarily comes from flouorophilic‐σ‐lock (~70%) contributions. These interactions are significantly diminished for non‐self‐healable counterparts. Strongly polarized ‐C‐F σ orbitals create lateral dipolar forces enhancing the affinity towards ‐C‐H orbitals, facilitating energetically favorable interactions. Entropic recovery driven by non‐covalent bonding offers a valuable tool in designing materials with unique functionalities, particularly self‐healable batteries or other energy storage devices.

中文翻译：

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亲氟西格玛(σ)锁自修复共聚物

尽管含氟分子和大分子经常用于分子生物学中，通过引入有利的 C-F 偶极子来增加与路易斯酸性基团的结合，但实际上没有实验证据，对这些相互作用的性质的了解也很有限，特别是它们在合成中的作用高分子材料。这些研究阐明了由五氟苯乙烯和丙烯酸正丁酯单元 (p(PFS/nBA) 组成的含氟共聚物 (p(PFS/nBA)) 进行自修复的链间和链内相互作用的分子起源。以动态表面振荡力 (SOF) 为指导和分子动力学（MD）模拟支持的光谱测量，这些研究表明，nBA单元的PFS和CH3CH2-的-C-F中σ-σ轨道的重组能够通过亲氟-σ-lock van der恢复熵能当 PFS/nBA 摩尔比约为 50/50 时的华耳斯力 通过实验确定的可自修复 PFS/nBA 组合物的相互作用强度约为 0.3 kcal/mol，主要来自亲氟-σ-锁（约 70）。对于非自修复对应物，这些相互作用显着减少，强极化的 ‐C-F σ 轨道产生横向偶极力，增强了对 ‐C-H 轨道的亲和力，促进了能量上有利的相互作用。非共价键驱动的熵恢复为设计具有独特功能的材料提供了宝贵的工具，特别是自修复电池或其他储能设备。