Postsynthetically Modified Alkoxide‐Exchanged Ni2(OR)2BTDD: Synergistic Interactions of CO2 with Open Metal Sites and Functional Groups

Abstract Postsynthetic modifications (PSMs) of metal–organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in Ni 2 Cl 2 BTDD (BTDD=bis (1H‐1,2,3,–triazolo [4,5‐b],–[4′,5′‐i]) dibenzo[1,4]dioxin) through PSM. Rietveld refinement of synchrotron X‐ray diffraction data indicated that the alkoxide oxygen atom bridges Ni(II) centers while the OMSs of the MOF are preserved. Due to the synergy of the existing OMS and introduced functional group, the alkoxide‐exchanged MOFs showed CO 2 uptakes superior to the pristine MOF. Remarkably, the tert‐butoxide‐substituted Ni_T exhibited a nearly threefold and twofold increase in CO 2 uptake compared to Ni 2 Cl 2 BTDD at 0.15 and 1 bar, respectively, as well as high water stability relative to the other exchanged frameworks. Furthermore, the Grand Canonical Monte Carlo simulations for Ni_T suggested that CO 2 interacts with the OMS and the surrounding methyl groups of tert‐butoxide groups, which is responsible for the enhanced CO 2 capacity. This work provides a facile and unique synthetic strategy for realizing a desirable OMS‐incorporating MOF platform through bridging ligand exchange.