title: CuN6 Jahn-Teller centers in coordination frameworks comprising fully condensed Kuratowski-type secondary building units: phase transitions and magneto-structural correlations.
abstract: The metal-organic framework [Cu(ta)(2)] (Hta = 1H-1,2,3-triazole), containing Jahn-Teller active Cu(II) ions and 1,2,3-triazolate ligands, is prepared under solvothermal reaction conditions. The compound shows a reversible phase transition from the tetragonal crystal system (α-[Cu(ta)(2)]: space group I4(1)/amd (no. 141), a = 11.8447(7) Å, c = 18.9782(13) Å, V = 2662.6(3) Å(3)) to the cubic crystal system (β-[Cu(ta)(2)]: space group Fd3m (no. 227), a = 17.4416(15) Å, V = 5305.9(8) Å(3)) within the temperature range of 120-160 °C. Both [Cu(ta)(2)] polymorphs have identical bonding topologies that might be described as fully condensed Kuratowski-type pentanuclear secondary building units of local T(d) point group symmetry in which four Cu(II) ions occupy the vertices of an imaginary tetrahedron. α-[Cu(ta)(2)], as opposed to the high-temperature β-phase, shows a strong tetragonal Jahn-Teller distortion of CuN(6) coordination octahedra. The compounds are characterized by elemental and thermogravimetric analyses, single crystal and powder X-ray diffraction, FTIR-, UV-vis and fluorescence spectroscopy. Magnetic susceptibility investigations reveal two different Cu(II) sites at a ratio of 1 : 2, in agreement with the solid state structure of [Cu(ta)(2)]. At low temperatures the formation of antiferromagnetically coupled Cu(II) dimers is observed, leading to a spin frustration of roughly 1/3 of all magnetically active Cu(II) sites.
authors.affiliation: Institute of Physics, Chair of Solid State and Materials Chemistry, Augsburg University, Universitätstraβe 1, 86159 Augsburg, Germany.
authors.forename: Maciej
authors.initials: M
authors.lastname: Grzywa
authors.forename: Dmytro
authors.initials: D
authors.lastname: Denysenko
authors.forename: Jan
authors.initials: J
authors.lastname: Hanss
authors.forename: Ernst-Wilhelm
authors.initials: EW
authors.lastname: Scheidt
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Scherer
authors.forename: Matthias
authors.initials: M
authors.lastname: Weil
authors.forename: Dirk
authors.initials: D
authors.lastname: Volkmer