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Different Breathing Mechanisms in Flexible Pillared-Layered Metal-Organic Frameworks − Impact of the Metal Center

DOI: 10.1021/acs.chemmater.7b05052 DOI Help

Authors: Andreas Schneemann (Ruhr-Universität Bochum; Technische Universität München) , Pia Vervoorts (Technische Universität München) , Inke Hante (Ruhr-Universität Bochum) , Min Tu (Ruhr-Universität Bochum; KU Leuven) , Suttipong Wannapaiboon (Ruhr-Universität Bochum; Technische Universität München) , Christian Sternemann (Technische Universität Dortmund) , Michael Paulus (Technische Universität Dortmund) , D. C. Florian Wieland (Technische Universität Dortmund; Helmholtz-Zentrum Geesthacht) , Sebastian Henke (Technische Universität Dortmund) , Roland A. Fischer (Technische Universität München)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: February 2018
Diamond Proposal Number(s): 9225

Abstract: The pillared-layered metal-organic framework compounds M2(BME-bdc)2(dabco) (M2+ = Zn2+, Co2+, Ni2+, Cu2+; BME-bdc2- = 2,5-bis(2-methoxyethoxy)-1,4-benzenedicarboxylate; dabco = diazabicyclo[2.2.2]octane) exhibit structural flex-ibility 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 tem-perature), 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 lig-and field effects on the coordination bonds. Accordingly, in situ PXRD measurements as a function of CO2 pressure reveal different mechanisms for the np to lp phase transition during CO2 adsorption.

Subject Areas: Materials, Chemistry

Instruments: I11-High Resolution Powder Diffraction

Other Facilities: DELTA Dortmund

Added On: 19/02/2018 08:43

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