Pore Engineering in Isoreticular Titanium‐Isophthalate Coordination Polymers

Abstract Pore engineering through chemical environment modification is vital for developing industrial porous materials. Understanding the effects of substitutions in isoreticular porous coordination polymers—such as steric hindrance, vibrational capabilities, electronic influences, and hydropathy—is key to elucidating structure–property relationships. However, accurately assessing the impact of functional groups on properties remains challenging due to limitations in current methodologies. In this study, we designed a series of titanium‐isophthalate coordination‐polymers with various functional groups to regulate pore characteristics and structural dimensionality. The unique spatial arrangement and electronic distribution of isophthalate and its functional groups provide an ideal platform to address these challenges. We conducted extensive investigations combining experimental methods with computational simulations to explore how pore engineering affects adsorptive separation and photoresponsive behavior in these compounds. Our findings not only tackle the synthesis challenge of isostructural titanium‐coordination polymers but also offer new insights into understanding structure–property relationships achieved through modulation of their chemical environments.