Chemoselectivity Inversion of Responsive Metal–Organic Frameworks by Particle Size Tuning in the Micrometer Regime

Gated adsorption is one of the unique physical properties of flexible metal–organic frameworks with high application potential in selective adsorption and sensing of molecules. Despite recent studies that have provided some guidelines in understanding and designing structural flexibility for controlling gate opening by chemical modification of the secondary building units, currently, there is no established strategy to design a flexible MOF showing selective gated adsorption for a specific guest molecule. In a present contribution it is demonstrated for the first time, that the selectivity in the gate opening of a particular compound can be tuned, changed, and even reversed using particle size engineering DUT‐8(Zn) ([Zn2(2,6‐ndc)2(dabco)]n, 2,6‐ndc = 2,6‐naphthalenedicarboxylate, dabco = 1,4‐diazabicyclo‐[2.2.2]‐octane, DUT = Dresden University of Technology) experiences phase transition from open (op) to closed (cp) pore phase upon removal of solvent from the pores. Microcrystals show selective reopening in the presence of dichloromethane (DCM) over alcohols. Crystal downsizing to micron size unexpectedly reverses the gate opening selectivity, causing DUT‐8(Zn) to open its nanosized pores for alcohols but suppressing the responsivity toward DCM. In the flexible DUT‐8(Zn) metal–organic framework, the selective triggering of gate opening can be adjusted, altered, and even reversed through particle size engineering. Macrosized crystals exhibit selective opening in the presence of dichloromethane (DCM) over alcohols. Downsizing crystals to the micron size reverses gate opening selectivity, causing DUT‐8(Zn) to open its pores for alcohols while suppressing its responsiveness toward DCM.