Ultra-fine structural tuning of metal-organic frameworks (MOFs) using isoreticular chemistry is helpful in designing ideal gas adsorbents but is extremely challenging. Known strategies mainly focus on ligand substitution/modification. Here, we open a pathway, metal-cluster-powered ultramicropore alliance, based on the pacs (partitioned acs) platform. The half replacement of Mn₃ clusters by Mn₆ clusters endows the target SNNU-181-Mn₃₊₆, the first case of multi-cluster based pacs MOF, with combined ultramicropore as well as finely optimized N sites, resulting in greatly improved performance and setting a benchmark for challenging one-step ethylene (C₂H₄) purification. With the highest C₂H₆ uptake (5.49 mmol g⁻¹), record-high C₂H₂ uptake (5.95 mmol g⁻¹), and satisfactory ideal adsorbed solution theory (IAST) selectivity, SNNU-181-Mn₃₊₆ can afford top-level C₂H₄ productivity under ambient conditions. Supported by the isoreticular replacement of the metal cluster module, the ultramicropore alliance breaks new ground in MOF chemistry.

使用等网化学对金属有机框架（MOF）进行超精细结构调整有助于设计理想的气体吸附剂，但极具挑战性。已知的策略主要集中于配体取代/修饰。在这里，我们开辟了一条基于pacs（分区acs）平台的金属簇驱动超微孔联盟途径。 Mn ₆团簇一半取代 Mn ₃团簇，赋予了目标 SNNU-181-Mn ₃₊₆，这是基于多团簇的pacs MOF 的第一个案例，具有组合的超微孔以及精细优化的 N 位点，从而大大提高了性能并为具有挑战性的一步乙烯（C ₂ H ₄）纯化设定基准。 SNNU-181-Mn ₃₊具有最高的 C ₂ H ₆吸收率（5.49 mmol g ^-1）、创纪录的 C ₂ H ₂吸收率（5.95 mmol g ^-1）和令人满意的理想吸附溶液理论（IAST）选择性。₆可以在环境条件下提供顶级的C ₂ H ₄生产率。在金属簇模块等网状取代的支持下，超微孔联盟在 MOF 化学领域开辟了新天地。