Nature controls the assembly of complex architectures through self-limiting processes; however, few artificial strategies to mimic these processes have been reported to date. Here we demonstrate a system comprising two types of nanocrystal (NC), where the self-limiting assembly of one NC component controls the aggregation of the other. Our strategy uses semiconducting InP/ZnS core–shell NCs (3 nm) as effective assembly modulators and functional nanoparticle surfactants in cucurbit[n]uril-triggered aggregation of AuNCs (5–60 nm), allowing the rapid formation (within seconds) of colloidally stable hybrid aggregates. The resultant assemblies efficiently harvest light within the semiconductor substructures, inducing out-of-equilibrium electron transfer processes, which can now be simultaneously monitored through the incorporated surface-enhanced Raman spectroscopy–active plasmonic compartments. Spatial confinement of electron mediators (for example, methyl viologen (MV²⁺)) within the hybrids enables the direct observation of photogenerated radical species as well as molecular recognition in real time, providing experimental evidence for the formation of elusive σ–(MV⁺)₂ dimeric species. This approach paves the way for widespread use of analogous hybrids for the long-term real-time tracking of interfacial charge transfer processes, such as the light-driven generation of radicals and catalysis with operando spectroscopies under irreversible conditions.

自然通过自我限制过程控制复杂架构的组装；然而，迄今为止，几乎没有报道过模拟这些过程的人工策略。在这里，我们展示了一个由两种类型的纳米晶体 (NC) 组成的系统，其中一个 NC 组件的自限组装控制另一个 NC 组件的聚集。我们的策略使用半导体 InP/ZnS 核壳 NC（3 nm）作为葫芦中的有效组装调节剂和功能性纳米颗粒表面活性剂[ n]uril 触发的 AuNCs 聚集（5-60 nm），允许快速形成（在几秒钟内）胶体稳定的混合聚集体。由此产生的组件有效地收集半导体子结构内的光，诱导失衡的电子转移过程，现在可以通过结合的表面增强拉曼光谱-活性等离子体隔室同时监测。电子介体（例如，甲基紫精（MV ²⁺））在杂化体内的空间限制能够直接观察光生自由基种类以及实时分子识别，为难以捉摸的σ -（MV ⁺ ）的形成提供实验证据) ₂二聚体。这种方法为广泛使用类似的混合材料来长期实时跟踪界面电荷转移过程铺平了道路，例如在不可逆条件下光驱动自由基的产生和操作光谱催化。