0000000000146802
AUTHOR
Wolfgang Linert
Spin crossover in iron(II) tris(2-(2′-pyridyl)benzimidazole) complex monitored by variable temperature methods: synchrotron powder diffraction, DSC, IR spectra, Mössbauer spectra, and magnetic susceptibility
Abstract The thermal expansion of the spin crossover system [Fe(pybzim) 3 ](ClO 4 ) 2 · H 2 O (pybzim=2-(2 ′ -pyridyl)benzimidazole) has been determined from powder X-ray data between 50 and 250 K; the wavelength of the synchrotron source was 1.21888(1) A. The unit cell parameters of the triclinic crystal system were a =12.091 A, b =12.225 A, c =14.083 A, α =77.70°, β =80.35°, γ =74.35°, and V =1944.9 A 3 at 250 K. In addition to the linear thermal expansion of the unit cell volume, an extra expansion due to the low-spin (LS) to high-spin (HS) transition is observed. The V ( T ) function shows a sudden increase comparable with the step in the effective magnetic moment at the transition reg…
Synthesis and characterisation of tetrazole compounds: 3 series of new ligands representing versatile building blocks for iron(II) spin-crossover compounds
Abstract New tetrazole compounds were synthesized and characterised by NMR and FTIR spectroscopy as well as by single crystal X-ray diffraction. We present in this paper mono- and ditetrazoles, which represent a versatile class of building blocks for the formation of mononuclear iron(II) complexes with monotetrazoles as terminal ligands as well as iron(II) coordination polymers with ditetrazoles as bridging ligands. Especially, the series of α,ω-bis[tetrazol-1-yl]-alkanes open the field of fascinating supramolecular structures with spin transition properties.
Tuning the spin crossover above room temperature: iron(II) complexes of substituted and deprotonated 2,6-bis(benzimidazol-2-yl)pyridine
Abstract The complex [Fe(tzimpy)2](ClO4)2 · 2H2O (tzimpy = 2,4,6-tris-(benzimidazol-2-yl)pyridine) shows an abrupt spin crossover (S = 0–2 transition) above room temperature centered at Tc = 323 K with a hysteresis width of ΔT = 35 K. The neutral iron(II) complex with deprotonated bzimpy ligands (bzimpy = 2,6-bis(benzimidazol-2-yl)pyridine) exhibits a gradual spin transition on the first heating with Tc = 424 K. There are irreversible changes between T = 503 and 523 K: the liberation of the crystal water, the color change (blue–green) followed by a structure change. Next thermal cycles are reproducible though, heating/cooling paths are different from the first heating.
Structure and physical properties of [mu-tris(1,4-bis(tetrazol-1-yl)butane-N4,N4 ')iron(II)] bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice
[mu-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4')iron(II)] bis(hexafluorophosphate), [Fe(btzb)(3)](PF6)(2), crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T-1/2 = 174 K and a hysteresis of about 4 K between T-1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, Fe-57-Mossbauer spectroscopy, and variable temperature far and midrange FIR spectroscopy. The title compound crystallizes in the trigonal space group P (3) over bar (No. 147) with a unit cell content of one formula u…
Synthesis, crystal structure and magnetic properties of [Cu(bipy)2(CH3COO)][Cu(bipy)2(Cr(C2O4)3)]·∼10.5H2O, the first compound containing the [Cr(C2O4)3]3− building block acting as a monodentate ligand
Abstract The reaction between copper(II) acetate with 2,2′-bipyridine and K3[Cr(C2O4)3] leads to the novel salt [Cu(bipy)2(CH3COO)][Cu(bipy)2(Cr(C2O4)3)]·∼10.5H2O, 1 (bipy=2,2′-bipyridine). The crystal structure of 1 consists of mononuclear cationic species [Cu(bipy)2(CH3COO)]+ and heterobinuclear anionic units, [Cu(bipy)2(Cr(C2O4)3)]−. The tris-oxalato-chromium entity behaves as a monodentate ligand toward the copper(II) ion within the complex anion. The distance between Cr(III) and Cu(II) across the bridging oxalato group is 5.056(2) A. The copper(II) ions exhibit a distorted trigonal bipyramidal surrounding in both cationic and anionic species. The π–π stacking interaction between bipy l…
Anisotropic Effect after Stretching of the Spin-Crossover Compound [Fe(II)(2,6-bis-(benzimidazol-2′-yl)pyridine)2] (C1O4)2 in Polyvinylalcohol Polymer Matrix
Abstract [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2](C1O4)2 diffused into a poly(vinyl)alcohol polymer matrix, exhibits an thermally induced spin-crossover. After stretching the matrix, the compound orients itself in the matrix. Polarised UV/VIS spectra measured parallel and perpendicular to the stretching direction allowed to calculate the distortion of the molecule in the matrix by means of semi-empirical PPP SCF-CI calculations.
Spin-Transition in [Fe(II)(2,6-Bis-(Benzimidazol-2′-yl)pyridine)2] (CIO4)2: Hysteresis Effect Dependent on the Matrix
Abstract Far-Infrared spectroscopical investigation of the spin-crossover in [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2] (CIO4)2 exhibits a hysteresis in both CsI and polyethylene matrices within temperature cycles between 100K and 520K. The hysteresis broadening is dependent on the matrix and bigger in CsI. This can be explained due to polarity and hydrogen bonding. Two low spin vibrations, LS1 at 437 cm−1 and LS2 at 424cm−1, are observed. On heating from 100K to 520K: during LS1 decreases, the LS2 raises temporarily, until both LS1 and LS2 disappear; for the HS only one raising species was observed. This gives raise to assume two different sub-lattices.
Spin crossover in mononuclear and binuclear iron(III) complexes with pentadentate Schiff-base ligands
Abstract A series of mononuclear hexacoordinate iron(III) complexes, [Fe( 5 L )(py)]BPh 4 , and binuclear hexacoordinate iron(III) complexes, [( 5 L )Fe(μ 2 -bpy)Fe( 5 L )](BPh 4 ) 2 , has been prepared and their magnetic properties were investigated; the pentadentate ligands were derivatives of 5 L =saldptn=N,N′-bis(2-hydroxybenzyliden)-1,7-diamino-4-azaheptane. Temperature variation of the effective magnetic moment for them shows that a spin transition from the low-spin to the high-spin state occurs. The magnetic data were fitted to an Ising-like model appropriate for the mono- and binuclear systems.
catena-[µ-Tris(1,2-bis(tetrazol-1-yl)ethane-N4,N4')iron(II)] bis(tetrafluoroborate): synthesis, structure, spectroscopic and magnetic characterization of a chain-type coordination polymer spin-crossover compound.
In analogy to a common synthesis of 1-substituted 5-H tetrazoles (Tetrahedron Lett. 36 (1995)1759; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 11 (1985) 1521; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 1 (1991) 66; BGU, Belarus. Vestsi Akad. Navuk Belarusi, Ser. Khim. Navuk 1 (1992) 73), the new bidentate ligand 1,2-bis(tetrazol-1-yl)ethane [endi] was synthesized and characterized by X-ray diffraction, NMR, IR and UV–Vis spectroscopy. By using iron(II) tetrafluoroborate hexahydrate the complexation with this ligand yields a 1-dimensional linear coordination polymer similar to the recently published chain compound (Inorg. Chem. 39 (2000) 1891) exhibiting …