Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications. Photoresponsive metal-organic polyhedra (PMOPs) feature intrinsic pores and remote controllability, but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously. Herein, we report the construction of a new PMOP (Cu₂₄(C₁₆H₁₂N₂O₄)₁₂(C₁₈H₂₂O₅)₁₂, denoted as MOP-PR-LA), where long alkyl (LA) chains act as the intermolecular poles, propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive (PR) moieties. Upon ultraviolet (UV)- and visible-light irradiation, MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA. For propylene adsorption, MOP-PR has a low change of adsorption capacity (9.9%), while that of MOP-PR-LA reaches 58.6%. Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption, while the trans state of PR favors adsorption. This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.

材料的光响应性对其在终端应用中的可调性和效率至关重要。光响应金属有机多面体（PMOPs）具有固有的孔隙和远程可控性，但PMOPs在固态下的聚集严重阻碍了其光响应性。在此，我们报道了一种新的PMOP（Cu ₂₄ (C ₁₆ H ₁₂ N ₂ O ₄ ) ₁₂ (C ₁₈ H ₂₂ O ₅ ) ₁₂，表示为MOP-PR-LA）的构建，其中长烷基（LA）链作为分子间极，支撑相邻的 PMOP 分子，创造有利于光响应 (PR) 部分异构化的个体微环境。在紫外线 (UV) 和可见光照射下，MOP-PR-LA 比不含 LA 的对应 MOP-PR 更容易异构化。对于丙烯吸附，MOP-PR的吸附容量变化较低（9.9%），而MOP-PR-LA的吸附容量变化达到58.6%。密度泛函理论计算表明，顺式状态下的PR对吸附有负面影响，而反式状态下的PR有利于吸附。这项工作可能为构建具有高响应性和可控性的光响应材料开辟一条途径。