The ability of metal organic frameworks (MOFs) to modulate the photophysical properties of encapsulated guests is of importance for the applications of these materials in light harvesting and photocatalysis. Here, the photophysical properties of tetra (N-methyl-4-pyridyl)-21H,23H porphine (TMPyP) encapsulated within two Cd-based MOFs (MOM-11 and MOM-12) are reported. It is shown that the pores of [email protected] [email protected] fix the orientation of the porphyrin peripheral pyridinium groups relative to the porphyrin plane. These fixed orientations have a significant effect on the porphyrin S₁-CT coupled excited state leading to differences in steady state emission, emission lifetimes, and absorption properties. In addition, it is observed that the pores [email protected] [email protected] also restrict out of plane porphyrin ring distortions associated with sit-atop porphyrins resulting in extended triplet state lifetimes. The results demonstrate that specific pore structures can systematically modulate the excited state properties of TMPyP type porphyrins by regulating accessible guest conformations.

金属有机骨架（MOF）调节封装客体光物理性质的能力对于这些材料在光收集和光催化中的应用至关重要。在这里，报道了封装在两个基于Cd的MOF（MOM-11和MOM-12）中的四（N-甲基-4-吡啶基）-21H，23H卟啉（TMPyP）的光物理性质。结果表明，[受电子邮件保护] [受电子邮件保护]的孔固定了卟啉外围吡啶鎓基团相对于卟啉平面的取向。这些固定的方向对卟啉S ₁有重要影响-CT耦合激发态导致稳态发射，发射寿命和吸收特性的差异。另外，观察到[受电子邮件保护] [受电子邮件保护]的孔还限制了与坐位卟啉相关的平面外卟啉环变形，从而延长了三重态的寿命。结果表明，特定的孔结构可以通过调节可及的客体构象，系统地调节TMPyP型卟啉的激发态性质。