Organically templated polar metal oxyfluorides

• Applicant: Professor Dr. Harald Krautscheid
• Subject Area: Solid State and Surface Chemistry, Material Synthesis ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2016 to 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 325510855

• Final Report Year: 2021

Final Report Abstract

1) A series of bipyrazole species representing CH3, NH2, NO2 functionalized 4,4'-bipyrazoles and their extended analogs with phenylene and biphenyl spacer units were developed as a new family of versatile molecular building blocks for crystal engineering of coordination polymers. In the light of our findings, the airand moisture-tolerating cycloaddition reactions of diazo compounds could be proposed as practical methodology for the pyrazolyl functionalization of aromatic substrates. High-yielding and selective polynitrations at the 4,4'-bipyrazole backbone and subsequent reductions to amino derivatives provide an easy access to libraries of polyfunctional pyrazole ligands. 2) Pyrazoles are excellent building blocks for the construction of polar 1D coordination chains incorporating non-centrosymmetric oxofluorometalate units as co-ligands. Special orientations of these anions are achieved by hydrogen bonding through NH-sites of the pyrazole ligands. Such dual functionality was a key for successful engineering of unprecedented 1D coordination polymers [M II(L)4{MVOF5}]n (MII = Cu, Zn, Cd; MV = Nb, Ta; L = 3,5- and 3,4,5-substituted pyrazoles) with a concerted and coherent alignment of [MOF 5]2- units along the chains and, thus, every individual molecular dipole additively contributes to the net dipole moment of the coordination linkage. We have shown that unambiguous evidence for orientational order of [MOF5]2- in crystal structures requires mean square displacement amplitude analysis of thermal motion. 3) The coordination chains mentioned above are applicable for construction of 3D framework coordination polymers as a special kind of subunits of lower dimensionality. With a doubled pyrazole functionality of the organic ligand (4,4-bipyrazoles and their extended analogs), the inorganic connectivity –(M II-OMVF5)n-MII– remains intact, while covalent links between two pyrazole halves provide connectivity between the chains. A variety of frameworks [MII(Me4bpz)2{MVOF5} ∙ Guest]n (Guests are substituted aromatic species) revealed how the polar symmetry of such subunits may be imprinted into the overall symmetry of the 3D lattice. Most of such compounds crystallize in polar or chiral space groups, depending on the guest template, and the concerted alignment of [MVOF5]2- dipoles is important for elimination of inversion symmetry. 4) The special templating function of coordinatively unsaturated [M II(pyrazole)4]2+ units (as donors of multiple hydrogen bonds) could be essential for supramolecular synthesis in fluoride systems, which reveals a versatility of polynuclear Ta oxofluoride patterns. Mild hydrolysis of [TaOF5]2- allows preparation of polyhedral species, such as [Ta6O9F18]6- and [Ta8O12F24]8- isolable in the dense environment of M II- pyrazole cations. 5) Studies of crystal structure and thermal stability of the compounds revealed a unique behaviour of [Cu(L)4{MVOF5}]n systems, polymerization isomerism: Polymers [Cu(3,5-Me2pz)4{MVOF5}]n (MV = Nb, Ta) irreversibly depolymerize above 180 oC without loss of crystallinity. 3D lattices based upon oxofluorides show excellent thermal stability. Elimination of guest molecules from the clathrates [M II(Me4bpz)2{MVOF5} ∙ Guest]n proceeds at 100-200 °C, while the desolvated frameworks are stable up to 320 °C. These features are relevant for preparation of permanently porous chiral or polar lattices for applications in adsorption.

Publications

• Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4- triazole) Ligand: A Look through the Composition-Space Diagram. Inorg. Chem. 56 (2017), 12952-12966
  G. A. Senchyk, A. B. Lysenko, K. V. Domasevitch, O. Erhart, S. Henfling, H. Krautscheid, E. B. Rusanov, K. W. Krämer, S, Decurtins, S.-X. Liu
  
• Triazolyl, Imidazolyl, and Carboxylic Acid Moieties in the Design of Molybdenum Trioxide Hybrids: Photophysical and Catalytic Behavior. Inorg. Chem. 56 (2017), 4380-4394
  A. B. Lysenko, G. A. Senchyk, K. V. Domasevitch, M. Kobalz, H. Krautscheid, J. Cichos, M. Karbowiak, P. Neves, A. A. Valente, I. S. Gonçalves
  
• Face-to-face stacking of caffeinium and [PMVI12O40] 3− ions: A synthon for crystal engineering with purine bases. Inorg. Chem. Commun. 94 (2018), 119-122
  O. S. Panteleieva, A. V. Shtemenko, K. V. Domasevitch
  
• Making an order: the concerted alignment of [MOF5]2− (M = Nb and Ta) dipolar anions in onedimensional coordination chains sustained by tris(3,4,5-trimethyl-1H-pyrazole)copper(II). Acta Crystallogr. Section C: Struct. Chem. 74 (2018) 929-935
  A. V. Sharko, O. Erhart, H. Krautscheid, K. V. Domasevitch
  
• A Molybdenum Trioxide Hybrid Decorated by 3-(1,2,4-Triazol-4-yl)adamantane-1-carboxylic Acid: A Promising Reaction-Induced Self-Separating (RISS) Catalyst. Inorg. Chem. 58 (2019), 16424-16433
  A. B. Lysenko, G. A. Senchyk, K. V. Domasevitch, S. Henfling, O. Erhart, H. Krautscheid, P. Neves, A. A. Valente, M. Pillinger, I. S. Gonçalves
  
• Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials. New J. Chem. 43 (2019) 1305-1312
  K. V. Domasevitch, I. Gospodinov, H. Krautscheid, T. M.Klapötke, J. Stierstorfer
  
• Bulk polarity of 3, 5, 7-trinitro-1-azaadamantane mediated by asymmetric NO 2 (lone pair) ··NO2 (-hole) supramolecular bonding. Acta Crystallogr. Section C: Struct. Chem. 76 (2020) 598-604
  K. V. Domasevitch, G. A. Senchyk, H. Krautscheid
  
• Control over the coordination preferences in Ag+ and Ag+/UO22+ 1, 2, 4-triazolecarboxylate frameworks. Inorg. Chem. Commun. 113 (2020) 107813
  G. A. Senchyk, A. B. Lysenko, H. Krautscheid, K. V. Domasevitch
  
• Crystal structure and Hirshfeld surface analysis of 4, 4′-(propane-1, 3-diyl) bis (4H-1,2,4-triazol-1-ium) pentafluoridooxidovanadate(V). Acta Crystallogr. Sect. E: Crystallogr. Commun. 76 (2020) 780-784
  G. A. Senchyk, A. B. Lysenko, H. Krautscheid, K. V. Domasevitch
  
• Dithiol-dithione tautomerism of 2,3-pyrazinedithiol in the synthesis of new copper and silver coordination compounds. Inorg. Chem. 59 (2020) 16441
  S. Henfling, R. Kempt, J. Klose, A. Kuc, B. Kersting, H. Krautscheid
  
• 1D, 2D, and 3D Coordination Polymers based on 2,3-Pyrazinedithiolate and d 10 Metal Ions (Ag+, Zn2+). Z. anorg. allg. Chem. (2021)
  S. Henfling, O. A. Saputra, H. Krautscheid
  
• Proton and Electron Transfer in the Formation of a Copper Dithiolene-Based Coordination Polymer. Inorg. Chem. 60 (2021) 9008-9018
  S. Henfling, A. Kultaeva, A. Pöppl, J. Klose, B. Kersting, K. V. Domasevitch, H. Krautscheid