Structural Transitions of the Metal–Organic Framework DUT-49(Cu) upon Physi- and Chemisorption Studied by in Situ Electron Paramagnetic Resonance Spectroscopy

Flexible metal–organic frameworks (MOFs) exhibit a variety of phenomena attractive for basic and applied science. DUT-49(Cu) is one of the remarkable representatives of such MOFs, where phase transitions are coupled to pressure amplification and “negative gas adsorption”. In this work we report important insights into structural transitions of DUT-49(Cu) upon physi- and chemisorption of gases and volatile liquids obtained by in situ electron paramagnetic resonance (EPR) spectroscopy. In this method, phase transitions are detected via the zero-field splitting in dimeric copper(II) units. First, a new approach was validated upon physisorption of n-butane. Then, using diethyl ether, we for the first time demonstrated that chemisorption can also trigger phase transition in DUT-49(Cu). On the basis of the EPR results, the transition appears completely reversible. The developed EPR-based approach can also be extended to other flexible MOFs containing paramagnetic metal paddlewheels, where high sensitivity and spectral resolution allow in situ studies of stimuli-induced structural variability.

[1]  M. Fedin,et al.  Mitigation of Pressure-Induced Amorphization in Metal-Organic Framework ZIF-8 upon EPR control. , 2020, ACS applied materials & interfaces.

[2]  S. Krause,et al.  Impact of Defects and Crystal Size on Negative Gas Adsorption in DUT-49 Analyzed by In Situ129Xe NMR Spectroscopy , 2020, Chemistry of materials : a publication of the American Chemical Society.

[3]  S. Krause,et al.  Tunable Flexibility and Porosity of the Metal–Organic Framework DUT-49 through Postsynthetic Metal Exchange , 2019, Chemistry of materials : a publication of the American Chemical Society.

[4]  M. Fedin,et al.  Precise Measurement and Controlled Tuning of Effective Window Sizes in ZIF-8 Framework for Efficient Separation of Xylenes. , 2019, Nano letters.

[5]  S. Krause,et al.  High-Pressure in Situ 129Xe NMR Spectroscopy: Insights into Switching Mechanisms of Flexible Metal–Organic Frameworks Isoreticular to DUT-49 , 2019, Chemistry of materials : a publication of the American Chemical Society.

[6]  M. Fedin,et al.  Radical-Doped Metal-Organic Framework: Route to Nanoscale Defects and Magnetostructural Functionalities. , 2019, Inorganic chemistry.

[7]  B. Martín‐Matute,et al.  Metal-Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective. , 2019, Journal of the American Chemical Society.

[8]  S. Kaskel,et al.  Synthesis and Characterization of Cu-Ni Mixed Metal Paddlewheels Occurring in the Metal-Organic Framework DUT-8(Ni0.98Cu0.02) for Monitoring Open-Closed-Pore Phase Transitions by X-Band Continuous Wave Electron Paramagnetic Resonance Spectroscopy. , 2019, Inorganic chemistry.

[9]  J. R. Schmidt,et al.  Flexible and Transferable ab Initio Force Field for Zeolitic Imidazolate Frameworks: ZIF-FF. , 2019, The journal of physical chemistry. A.

[10]  A. Schneemann,et al.  Probing Local Structural Changes at Cu2+ in a Flexible Mixed-Metal Metal-Organic Framework by in Situ Electron Paramagnetic Resonance during CO2 Ad- and Desorption , 2019, The Journal of Physical Chemistry C.

[11]  J. Caro,et al.  High-Flux High-Selectivity Metal-Organic Framework MIL-160 Membrane for Xylene Isomer Separation by Pervaporation. , 2018, Angewandte Chemie.

[12]  M. Weiss,et al.  Elucidating the Formation and Transformation Mechanisms of the Switchable Metal-Organic Framework ELM-11 by Powder and Single-Crystal EPR Study. , 2018, Inorganic chemistry.

[13]  Seda Keskin,et al.  High-Throughput Screening of MOF Adsorbents and Membranes for H2 Purification and CO2 Capture , 2018, ACS applied materials & interfaces.

[14]  O. Farha,et al.  A Flexible Metal-Organic Framework with 4-Connected Zr6 Nodes. , 2018, Journal of the American Chemical Society.

[15]  M. W. George,et al.  Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework , 2018, Nature Materials.

[16]  O. Farha,et al.  Catalytic chemoselective functionalization of methane in a metal−organic framework , 2018, Nature Catalysis.

[17]  S. Krause,et al.  The effect of crystallite size on pressure amplification in switchable porous solids , 2018, Nature Communications.

[18]  A. Huang,et al.  Smart Metal‐Organic Frameworks (MOFs): Switching Gas Permeation through MOF Membranes by External Stimuli , 2018 .

[19]  Chongli Zhong,et al.  Flexibility induced high-performance MOF-based adsorbent for nitroimidazole antibiotics capture , 2018 .

[20]  S. Rogge,et al.  Thermodynamic insight into stimuli-responsive behaviour of soft porous crystals , 2018, Nature Communications.

[21]  P. Heitjans,et al.  Defibrillation of soft porous metal-organic frameworks with electric fields , 2017, Science.

[22]  J. Long,et al.  A spin transition mechanism for cooperative adsorption in metal–organic frameworks , 2017, Nature.

[23]  S. Krause,et al.  In Situ Monitoring of Unique Switching Transitions in the Pressure-Amplifying Flexible Framework Material DUT-49 by High-Pressure 129Xe NMR Spectroscopy , 2017 .

[24]  François-Xavier Coudert,et al.  Origins of Negative Gas Adsorption , 2016 .

[25]  C. Detavernier,et al.  In Situ Electron Paramagnetic Resonance and X-ray Diffraction Monitoring of Temperature-Induced Breathing and Related Structural Transformations in Activated V-Doped MIL-53(Al) , 2016 .

[26]  S. Kaskel,et al.  EPR Insights into Switchable and Rigid Derivatives of the Metal–Organic Framework DUT-8(Ni) by NO Adsorption , 2016 .

[27]  M. Mendt,et al.  21. Electron Paramagnetic Resonance , 2016 .

[28]  A. Sheveleva,et al.  Mobility and Reactivity of 4-Substituted TEMPO Derivatives in Metal–Organic Framework MIL-53(Al) , 2016 .

[29]  François-Xavier Coudert,et al.  A pressure-amplifying framework material with negative gas adsorption transitions , 2016, Nature.

[30]  M. Ma̧czka,et al.  EPR Study of Structural Phase Transition in Manganese-Doped [(CH3)2NH2][Zn(HCOO)3] Metal–Organic Framework , 2015 .

[31]  Zhiyu Wang,et al.  Dual‐Emitting MOF⊃Dye Composite for Ratiometric Temperature Sensing , 2015, Advanced materials.

[32]  A. Corma,et al.  MOF catalysis in relation to their homogeneous counterparts and conventional solid catalysts , 2014 .

[33]  Qiang Xu,et al.  Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal-Organic Frameworks. , 2014, The journal of physical chemistry letters.

[34]  H. Doan,et al.  A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption , 2014, Materials.

[35]  Zhaoxiong Xie,et al.  MOF-templated synthesis of porous Co(3)O(4) concave nanocubes with high specific surface area and their gas sensing properties. , 2014, ACS applied materials & interfaces.

[36]  S. Sakaki,et al.  Interaction of various gas molecules with paddle-wheel-type open metal sites of porous coordination polymers: theoretical investigation. , 2014, Inorganic chemistry.

[37]  A. Gabrienko,et al.  Structural Dynamics in a "Breathing" Metal-Organic Framework Studied by Electron Paramagnetic Resonance of Nitroxide Spin Probes. , 2014, The journal of physical chemistry letters.

[38]  T. Maji,et al.  Temperature induced structural transformations and gas adsorption in the zeolitic imidazolate framework ZIF-8: a Raman study. , 2013, The journal of physical chemistry. A.

[39]  Alexander V. Neimark,et al.  Adsorption Deformation and Structural Transitions in Metal−Organic Frameworks: From the Unit Cell to the Crystal , 2013 .

[40]  Shubin Liu,et al.  Highly porous and stable metal–organic frameworks for uranium extraction , 2013 .

[41]  S. Krause,et al.  A highly porous metal-organic framework, constructed from a cuboctahedral super-molecular building block, with exceptionally high methane uptake. , 2012, Chemical communications.

[42]  A. Ghoufi,et al.  Large breathing of the MOF MIL-47(VIV) under mechanical pressure: a joint experimental–modelling exploration , 2012 .

[43]  Yern Seung Kim,et al.  MOF-Derived Hierarchically Porous Carbon with Exceptional Porosity and Hydrogen Storage Capacity , 2012 .

[44]  P. Nachtigall,et al.  Water Adsorption on Coordinatively Unsaturated Sites in CuBTC MOF , 2010 .

[45]  M. Hartmann,et al.  Structural Phase Transitions and Thermal Hysteresis in the Metal−Organic Framework Compound MIL-53 As Studied by Electron Spin Resonance Spectroscopy , 2010 .

[46]  Wei Zhou,et al.  Adsorption Sites and Binding Nature of CO2 in Prototypical Metal−Organic Frameworks: A Combined Neutron Diffraction and First-Principles Study , 2010 .

[47]  M. Fedin,et al.  Influence of the nature of organic components in dinuclear copper(II) pivalates on the composition of thermal decomposition products , 2010 .

[48]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

[49]  Randall Q. Snurr,et al.  Enhanced CO2 Adsorption in Metal-Organic Frameworks via Occupation of Open-Metal Sites by Coordinated Water Molecules , 2009 .

[50]  M. Hartmann,et al.  CW and Pulsed ESR Spectroscopy of Cupric Ions in the Metal−Organic Framework Compound Cu3(BTC)2 , 2008 .

[51]  S. Kaskel,et al.  Characterization of the metal-organic framework compound Cu3(benzene 1,3,5-tricarboxylate)2 by means of 129Xe nuclear magnetic and electron paramagnetic resonance spectroscopy. , 2006, The journal of physical chemistry. B.

[52]  A. Fletcher,et al.  Flexibility in metal-organic framework materials: impact on sorption properties , 2005 .

[53]  R. Belford,et al.  Quadrupole coupling constants of square-planar copper(II)-sulfur complexes from single-crystal electron paramagnetic resonance spectroscopy , 1976 .

[54]  J. Ammeter,et al.  Influence of the Host Lattice upon EPR Coupling Parameters and d‐d Transitions of Planar Copper (II) Complexes , 1972 .

[55]  Qiang Xu,et al.  Nanomaterials derived from metal–organic frameworks , 2018 .

[56]  Arthur Schweiger,et al.  EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. , 2006, Journal of magnetic resonance.