Matthias Grunert

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 a thermally induced spin-crossover phenomenon. Similar to the 1,2-bis(tetrazol-1-yl)propane-bridged compound, our 1,2-bis(tetrazol-1-yl)ethane-bridged compound shows a gradual spin transition, but the spin-crossover temperature T1/2≈140 K is found to be 10 K above the other T1/2. The T1/2 was determined by temperature-dependent 57Fe-Mossbauer, far FT-IR and UV–Vis spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Single crystals of the complex were grown in situ from a solution of the ligand and iron(II) tetrafluoroborate. The X-ray structure determinations of both the high spin as well as the low spin state of the compound revealed a solid state structure, which is comparable to that of catena-[Fe(1,2-bis(tetrazole-1-yl)propane)3](ClO4)2 (Inorg. Chem. 39 (2000) 1891; 2nd TMR-TOSS Meeting, 4th Spin Crossover Family Meeting, Lufthansa Training Center, Seeheim/Germany, April 30–May 2, 1999). Both the 1,2-bis(tetrazol-1-yl)propane-bridged and our compound do not show a thermal hysteresis effect (J. Am. Chem. Soc. 115 (1993) 9810; Inorg. Chim. Acta 37 (1979) 169; Chem. Phys. Lett. 93 (1982) 567). The synthesis of the complex described in the experimental section yielded a fine powdered product being poorly soluble in most common solvents. The single crystal measurements were done with crystals obtained by various diffusion methods. Most of them yielded either thin needles or small hexagonal prism crystals depending on the specific conditions.

Synthesis and thermal studies on iron(III) complexes of 4-N-(4′-antipyrylmethylidene)aminoantipyrine with varying counter ions

Abstract Iron(III) complexes of the Schiff base 4- N -(4′-antipyrylmethylidene)aminoantipyrine (AA) with counter ions, such as, perchlorate, nitrate, thiocyanate, chloride and bromide have been prepared and characterized by elemental analyses, electrical conductance in non-aqueous solvents, IR and electronic spectra, magnetic susceptibility measurements as well as by thermogravimetric analysis. The complexes have the general formulae [Fe(AA) 2 (ClO 4 )](ClO 4 ) 2 , [Fe(AA) 2 X 2 ]X (X=NO 3 − or Br − ) and [Fe(AA)X 3 ] (X=SCN − or Cl − ). In complexes, AA acts as a neutral bidentate ligand, coordinating through one of the carbonyl oxygens and azomethine nitrogen in perchlorate, nitrate and bromide complexes while the coordination of AA occurs in a neutral tridentate fashion through both carbonyl oxygens and azomethine nitrogen in thiocyanate and chloride complexes. In the perchlorate complex, one of the perchlorate ions is coordinated bidentately while in the nitrate complex two of the nitrate ions are coordinated monodentately to the metal ion. In the thiocyanate and chloride complexes all the anions are coordinated while in the bromide complex two of the bromide ions are coordinated. A high spin octahedral geometry is assigned to the iron(III) ion in all these complexes. The phenomenological, kinetic and mechanistic aspects of the nitrate, thiocyanate, chloride and bromide complexes were studied by TG and DTG techniques. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation were also computed. The rate controlling process in all stages of decomposition is random nucleation with one on each particle (Mampel model) [Thermochim. Acta 2 (1971) 423].

Antipyrine and its Derivatives with First Row Transition Metals

1

Linkage isomers of dibromobis(1-(2-methoxyethyl)tetrazole)copper(II) containing either a bromide or a unique tetrazole bridge

The ligand 1-(2-methoxyethyl)tetrazole (teeOMe) reacts with copper(II) bromide to form two different isomers with the formula [Cu(teeOMe)2Br2]n. The coordination details on the crystal packing are determined by the solvent from which the compound crystallises. In methanol, green crystals of α-[Cu(teeOMe)2Br2] (1) are formed, and these have been characterised by X-ray crystallography (at three temperatures) and magnetic susceptibility measurements. The crystal structure of 1 is built up from square-planar trans-[Cu(teeOMe)2Br2] units. Additional weak axial interactions between the copper centers and the N(2) tetrazole atoms of neighbouring complexes link the [Cu(teeOMe)2Br2] units into two-dimensional layers. Compound 1 displays paramagnetic behaviour (C = 0.41 cm3 K mol−1). In ethanol, yellow–brown crystals of β-[Cu(teeOMe)2Br2] (2) are formed, and these have been characterised by magnetic susceptibility measurements, in addition to IR, ligand field and EPR spectroscopy. The observed magnetic behaviour (C = 0.41 cm3 K mol−1, θ = 30.5 K and J/kB = 16.4 K) is consistent with a structure containing two-dimensional bromide-bridged copper(II) grids. It is proposed that in 2 the square-planar [Cu(teeOMe)2Br2] units are connected via axial Cu–Br interactions, as deduced from comparison of the magnetic properties.

Preparation and Radical Oligomerization of an Fe(II) Complex without Loss of Spin-Crossover Properties

11-(4H-1,2,4-Triazol-4-yl)-undecylmethacrylate (1), a new ligand for Fe(II) spin-crossover (SCO) complexes containing a polymerizable group, was synthesized and characterized. The complex [Fe·13](BF4)2 (2) was obtained by reaction of 1 with Fe(BF4)2·6H2O (molar ratio 1/Fe(II) = 3/1) in THF. Complex 2 showed a gradual spin-crossover between 80 and 230 K. The methacrylate units in the ligands of complex 2 could be oligomerized radically in solution (initiator: azoisobutyronitrile) without loss of the spin-crossover behaviour.