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| 电驱动铜纳米团簇耗散自组装 |
| Electrically Driven Dissipative Self-assembly of Copper Nanoclusters |
| 投稿时间：2026-07-07 修订日期：2026-07-30 |
| DOI： |
| 中文关键词: 耗散自组装 非平衡态 铜纳米团簇 超分子化学 动态材料 |
| 英文关键词:Dissipative self-assembly, non-equilibrium state, copper nanoclusters, supramolecular chemistry, dynamic materials |
| 基金项目:国家自然科学基金项目（52473115），上海市自然科学基金(25ZR1402373，23ZR1442700)、上海科技大学AI创新计划(AI2026B27)、上海科技大学“双一流”基金 |
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| 摘要点击次数: 51 |
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| 中文摘要: |
| 超分子耗散自组装利用热力学非平衡特性赋予材料动态可编程能力，是构筑智能材料的重要途径。尽管人工耗散自组装体系已取得一定进展, 但相较于生命体系, 其组装结构的精确性控制仍显不足。鉴于此, 本研究以原子级精确的铜纳米团簇为模型, 构建了电驱动的非平衡耗散自组装体系。在该体系中，一价铜 (CuI) 中心与二硫代氨基甲酸盐配体 (DTC) 组装形成金属-配体超分子团簇CuI6(DTC)6；停止电能供应后, CuI6(DTC)6自发氧化耗散为平衡态CuII前驱体, 再次注入电能可重启以上过程, 构成电能驱动的耗散循环。借助原位光谱跟踪、高分辨质谱、单晶X射线衍射、透射电镜等表征方法，揭示了金属-配体组装结构与演化机制, 并通过电压参数和氧气分压实现了对自组装与耗散动力学的调控。相较于化学燃料驱动体系, 电驱动耗散体系避免了燃料消耗造成的废物累积，可循环10次以上而无明显衰减, 展现出更高的循环稳定性。本工作通过电能驱动构建了一类结构达原子级精确的非平衡超分子自组装体系, 为动态超分子材料的精确构筑提供了新思路。 |
| 英文摘要: |
| Supramolecular dissipative self-assembly is an important approach that leverages thermodynamic non-equilibrium properties to endow materials with dynamic programming capabilities. Although artificial dissipative self-assembly systems have made some progress, they still lack structural precision compared to living systems. Therefore, this study uses atomically precise copper nanoclusters as a model to construct an electrically driven non-equilibrium dissipative self-assembly system. In this system, cuprous (CuI) centers assemble with dithiocarbamate ligands to form metal-ligand supramolecular clusters CuI6(DTC)6; Then the CuI6(DTC)6 are spontaneously oxidized by oxygen and dissipate into an equilibrium CuII precursor. Reintroducing electrical energy restarts the self-assembly process, thus constituting an electrically driven dissipation cycle. Using in situ UV-vis spectroscopy tracking, HR-MS, single-crystal X-ray diffraction (SC-XRD), and transmission electron microscopy (TEM), the metal-ligand assembly structures and their evolution mechanism were revealed, and the self-assembly and dissipation kinetics were regulated through the applied voltage and oxygen partial pressure. Compared with chemical fuel-driven systems, the electrically driven dissipative system avoids the waste accumulation caused by fuel consumption and can be cycled more than ten times without obvious decay, exhibiting superior cycling stability. This work establishes a class of non-equilibrium supramolecular self-assembly systems with atomically precise structures driven by electrical energy, providing a new strategy for the precise construction of dynamic supramolecular materials. |
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