Electric Field-Responsive Framework Materials from Aromatic Building Blocks

• Applicant: Professor Dr. Dirk Volkmer
• Subject Area: Solid State and Surface Chemistry, Material Synthesis
• Term: from 2019 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 426506525

• Final Report Year: 2024

Final Report Abstract

The objective of the project entitled “Electric Field-Responsive Framework Materials from Aromatic Building Blocks” was to develop electric-field excitable crystalline molecular materials and to test them for their usability in technical applications, such as gas separation, mechanical actuation or information storage technologies. By integrating electric field-dependent responses into novel framework designs, ferroelectric crystalline microporous polymers (F- CMPs) should be developed and proof-of-principle studies should demonstrate their technological potential. The envisaged systems included crystalline nanorotors, piezo-resonsive ferroelectrics, and nanoactuators comprising giant and/or ultrafast switching responses. The material design is based on porous frameworks (COFs or MOFs) containing e-field-responsive building units. Several chemically distinct classes of materials have been explored, with special emphasis being laid upon Kuratowski-type subunits, a secondary building unit forming the base for metal-organic framework compounds systematically developed at the University of Augsburg. All framework compounds have been investigated by standard methods of thermal analysis (TGA, DSC, VT-XRPD), porosity analysis (BET surface area) as well as by various spectroscopic techniques (UV-vis/NIR, FT-IR and/or Raman spectroscopy). Whenever possible framework compounds were tested with respect to external physical stimuli, such as static or alternating electric fields, in order to gain insight into dynamic structural changes of the framework lattices.

Publications

• docMOF 2018 - 1st European Doctoral Symposium on Metal-Organic Frameworks, 2018, Raitenhaslach, Germany, poster presentation, topic: “A 1,2,3-Triazolate-Based Kuratowski-Type Precursor for Novel Metal-Organic Framework Synthesis Approaches: Linkage of Prebuilt Secondary Building Units”
  Richard Röß-Ohlenroth
  
• euroMOF 2019 - 3rd International Conference on Metal Organic Frameworks and Porous Polymers, 2019, Paris, France, oral presentation, topic: “Organometallic MFU-4l(arge) Metal-Organic Frameworks”
  Richard Röß-Ohlenroth
  
• euroMof, 2019, 3rd International Conference on Metal Organic Frameworks and Porous Polymers, 2019, Paris, France, poster presentation (poster award), topic: "CFA-18: A newly developed homochiral metal-organic framework with an enantiopure rigid backbone triazolate ligand"
  Katharina Knippen
  
• Organometallic MFU-4l(arge) Metal–Organic Frameworks. Organometallics, 38(18), 3444-3452.
  Röß-Ohlenroth, Richard; Bredenkötter, Björn & Volkmer, Dirk
  
• CFA-18: a homochiral metal–organic framework (MOF) constructed from rigid enantiopure bistriazolate linker molecules. Dalton Transactions, 49(44), 15758-15768.
  Knippen, Katharina; Bredenkötter, Björn; Kanschat, Lisa; Kraft, Maryana; Vermeyen, Tom; Herrebout, Wouter; Sugimoto, Kunihisa; Bultinck, Patrick & Volkmer, Dirk
  
• Cooperative Large-Hysteresis Spin-Crossover Transition in the Iron(II) Triazolate [Fe(ta)2] Metal–Organic Framework. Inorganic Chemistry, 59(15), 10501-10511.
  Grzywa, Maciej; Röß-Ohlenroth, Richard; Muschielok, Christoph; Oberhofer, Harald; Błachowski, Artur; Żukrowski, Jan; Vieweg, Dana; von Nidda, Hans-Albrecht Krug & Volkmer, Dirk
  
• Acenaphtho[1,2‐d][1,2,3]triazole and Its Kuratowski Complex: A π‐Extended Tecton for Supramolecular and Coordinative Self‐Assembly. Chemistry – A European Journal, 28(4).
  Knippen, Katharina; Matuszczyk, Daniel; Kraft, Maryana; Bredenkötter, Björn; Eickerling, Georg; Lis, Tadeusz; Volkmer, Dirk & Stępień, Marcin
  
• Assembly of Porous Metal Hydrogen-Bonded Organic Frameworks from Diamine-Functionalized Kuratowski Complexes. Crystal Growth & Design, 22(1), 379-391.
  Röß-Ohlenroth, Richard; Freudig, Corbinian; Kraft, Maryana; Bunzen, Hana & Volkmer, Dirk
  
• euroMOF 2021 - 4th International Conference on Metal Organic Frameworks and Porous Polymers, 2021, virtual event, poster presentation, topic: “MFU-4-type Metal-Organic Frameworks with a Bidentate Bibenzimidazole Backbone for Postsynthetic Metalation”
  Richard Röß-Ohlenroth
  
• Advanced 1,2,3-Triazolate-Based Coordination Compounds: From Carbonic Anhydrase Mimics, Molecular Building Blocks, and Catalyst Supports to Electrically Conducting Spin-Crossover MOFs, 2022. Dissertation
  R. Roeß-Ohlenroth
  
• Combining Theory and Experiments To Study the Influence of Gas Sorption on the Conductivity Properties of Metal–Organic Frameworks. ACS Applied Materials & Interfaces, 14(29), 33662-33674.
  Muschielok, Christoph; Reiner, Alexander; Röß-Ohlenroth, Richard; Kalytta-Mewes, Andreas; Volkmer, Dirk; Wixforth, Achim & Oberhofer, Harald
  
• ICCC 2022 - 44th International Conference on Coordination Chemistry, 2022, Rimini, Italy, oral presentation, topic: “MFU-4-type Scaffolds Featuring Open Bidentate Bibenzimidazole Coordination Sites”
  Richard Röß-Ohlenroth
  
• Inhibition, Binding of Organometallics, and Thermally Induced CO Release in an MFU-4-Type Metal–Organic Framework Scaffold with Open Bidentate Bibenzimidazole Coordination Sites. Inorganic Chemistry, 61(41), 16380-16389.
  Röß-Ohlenroth, Richard; Kraft, Maryana; Bunzen, Hana & Volkmer, Dirk
  
• MOF 2022 - 8th International Conference on Metal-Organic Frameworks and Open Framework Compounds, 2022, Dresden, Germany, oral presentation, topic: “From Assembly of Metal Hydrogen-Bonded Organic Frameworks with Pre-Built Kuratowski SBUs towards Metal-Organic Framework Dyads”
  Richard Röß-Ohlenroth
  
• Synthesis, Thermal Stability and Magnetic Properties of an Interpenetrated Mn(II) Triazolate Coordination Framework. Zeitschrift für anorganische und allgemeine Chemie, 648(16).
  Röß‐Ohlenroth, Richard; Hirrle, Marcel; Kraft, Maryana; Kalytta‐Mewes, Andreas; Jesche, Anton; Krug, von Nidda Hans‐Albrecht & Volkmer, Dirk
  
• 2H NMR studies on the dynamics of supercooled water in a metal–organic framework. The Journal of Chemical Physics, 159(3).
  Schiller, Verena; Knippen, Katharina; Loidl, Alois; Lunkenheimer, Peter; Volkmer, Dirk & Vogel, Michael
  
• Frustration on a centered pyrochlore lattice in metal-organic frameworks. Physical Review Research, 5(2).
  Nutakki, Rajah P.; Röß-Ohlenroth, Richard; Volkmer, Dirk; Jesche, Anton; von Nidda, Hans-Albrecht Krug; Tsirlin, Alexander A.; Gegenwart, Philipp; Pollet, Lode & Jaubert, Ludovic D. C.
  
• Systematische Entwicklung und Charakterisierung neuartiger homochiraler Metall-Organischer Koordinationsverbindungen mit Azol-basierten Liganden, Universität Augsburg, 2023. Dissertation
  K. Knippen
  
• Unveiling the atomistic and electronic structure of NiII–NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling. Physical Chemistry Chemical Physics, 25(23), 15702-15714.
  Thangavel, Kavipriya; Bruzzese, Paolo Cleto; Mendt, Matthias; Folli, Andrea; Knippen, Katharina; Volkmer, Dirk; Murphy, Damien M. & Pöppl, Andreas
  
• Enantioselective enrichment of chiral 1-phenylethanol in the camphor-based chiral metal–organic framework CFA-22. CrystEngComm, 26(15), 2051-2055.
  Röβ-Ohlenroth, Richard; Knippen, Katharina; Kraft, Maryana & Volkmer, Dirk