Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E-def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E-def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E-def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E-def of PCP enables a selective gate-opening behavior toward CHCl3 over CH2Cl2 by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.