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The pillared-layered metal–organic framework compounds M₂(BME-bdc)₂(dabco) (M²⁺ = Zn²⁺, Co²⁺, Ni²⁺, Cu²⁺; BME-bdc^2– = 2,5-bis(2-methoxyethoxy)-1,4-benzenedicarboxylate; dabco = diazabicyclo[2.2.2]octane) exhibit structural flexibility and undergo guest and temperature-induced reversible phase transitions between a narrow pore (np) and a large pore (lp) form. These transitions were analyzed in detail by powder X-ray diffraction ex and in situ, isothermal gas adsorption measurements and differential scanning calorimetry. The threshold parameters (gas pressure or temperature), the magnitude of the phase transitions (volume change) as well as their transition enthalpies are strikingly dependent on the chosen metal cation M²⁺. This observation is assigned to the different electronic structures and ligand field effects on the coordination bonds. Accordingly, in situ powder X-ray diffraction measurements …