Radicals, with their unpaired electrons, exhibit unique chemical and physical properties that have long intrigued chemists. Despite early skepticism about their stability, the discovery of persistent radicals has opened new possibilities for molecular interactions. This review examines the mechanisms and applications of radically driven self‐assembly, focusing on key motifs such as naphthalene diimides, tetrathiafulvalenes, and viologens, which serve as models for radical assembly. The potential of radical interactions in the development of artificial molecular machines (AMMs) are also discussed. These AMMs, powered by radical‐radical interactions, represent significant advancements in non‐equilibrium chemistry, mimicking the functionalities of biological systems. From molecular switches to ratchets and pumps, the versatility and unique properties of radically powered AMMs are highlighted. Additionally, the applications of radical assembly in materials science are explored, particularly in creating smart materials with redox‐responsive properties. The review concludes by comparing AMMs to biological molecular machines, offering insights into future directions. This overview underscores the impact of radical chemistry on molecular assembly and its promising applications in both synthetic and biological systems.

中文翻译：

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利用自由基：自组装和分子机械的进展


自由基及其不成对的电子表现出独特的化学和物理性质，长期以来一直引起化学家的兴趣。尽管早期对其稳定性持怀疑态度，但持久性自由基的发现为分子相互作用开辟了新的可能性。这篇综述研究了自由基驱动自组装的机制和应用，重点关注作为自由基组装模型的关键基序，例如萘二酰亚胺、四硫富瓦烯和紫罗碱。还讨论了激进相互作用在人工分子机器（AMM）开发中的潜力。这些由自由基-自由基相互作用驱动的 AMM 代表了非平衡化学的重大进步，模仿了生物系统的功能。从分子开关到棘轮和泵，激进动力 AMM 的多功能性和独特性能得到了凸显。此外，还探索了自由基组装在材料科学中的应用，特别是在创建具有氧化还原响应特性的智能材料方面。该评论最后将 AMM 与生物分子机器进行了比较，提供了对未来方向的见解。本概述强调了自由基化学对分子组装的影响及其在合成和生物系统中的有前景的应用。