The capability to build up stable, switchable catalysts for complex artificial systems that can mimic the responsiveness of biological systems to multiple triggers is highly desirable and challenging. Herein, we engineer such a system by physically locking catalytically active metal clusters (MCs) inside individual cationic molecular organic cages (I-Cages), where the responsive and task-specific counteranions of I-Cages impart MCs with a programmable gating effect. This allows for precise spatial and temporal control over chemical reactions by regulating accessibility of reagents to the MC sites. Following this strategy, we have successfully tailored catalytic activity of a series of model catalysis (e.g., methanolysis of ammonia borane, and the reduction of 4-nitroaniline) by employing light and pH stimuli, as well as their combination, for programmable-activity control.

为复杂的人工系统构建稳定、可切换的催化剂的能力，可以模拟生物系统对多种触发的反应，这是非常可取的和具有挑战性的。在这里，我们通过将催化活性金属簇 (MC) 物理锁定在单个阳离子分子有机笼 (I-Cages) 内来设计这样一个系统，其中 I-笼的响应性和任务特定的反阴离子赋予 MC 可编程门控效应。这允许通过调节试剂对 MC 位点的可访问性来对化学反应进行精确的空间和时间控制。遵循这一策略，我们通过使用光和 pH 刺激以及它们的组合，成功地定制了一系列模型催化（例如氨硼烷的甲醇分解和 4-硝基苯胺的还原）的催化活性，