Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy.

A Sterically Hindered Derivative of 2,1,3-Benzotelluradiazole: A Way to the First Structurally Characterised Monomeric Tellurium-Nitrogen Radical Anion.

Interaction of the tetradentate redox-active 6,6'-[1,2-phenylenebis(azanediyl)]bis(2,4-di-tert-butylphenol) (H4 L) with TeCl4 leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN2 O2 fragment, which suggests the formulation of 1 as TeII L2- , in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp2 ] leads to quantitative formation of the paramagnetic salt [CoCp2 ]+ [1].- , which was characterised by single-crystal XRD. The solution EPR spectrum of [CoCp2 ]+ [1].- at room temperature features a quintet due to splitting on two equivalent 14 N nuclei. Below 150 K it turns into a broad singlet line with two weak satellites due to the splitting on the 125 Te nucleus. Two-component relativistic DFT calculations perfectly reproduce the a(14 N) HFI constants and A∥ (125 Te) value responsible for the low-temperature satellite splitting. Calculations predict that the additional electron in 1.- is localised mainly on L, while the spin density is delocalised over the whole molecule with significant localisation on the Te atom (≥30 %). All these data suggest that 1.- can be regarded as the first example of a structurally characterised monomeric tellurium-nitrogen radical anion.

3D molecular network and magnetic ordering, formed by multi-dentate magnetic couplers, bis(benzene)chromium(i) and [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl.

The reaction between bis(benzene)chromium(0), Cr0(C6H6)2, and [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (abbreviated as TDTD) formed single crystals of the 1 : 1 salt, [CrI(C6H6)2]+[TDTD]-. The crystal structure of [Cr(C6H6)2][TDTD] belongs to the monoclinic P21/c space group, and involves a CdSO4-type network (or quartz dual net), which is formed by CHN hydrogen bonds between [Cr(C6H6)2]+ (S = 1/2) and [TDTD]- (S = 1/2). In addition to this network, the two components form an alternating chain crystal with a π-π overlap along the [110] and [11[combining macron]0] directions. The theoretical calculations for the pairwise intermolecular magnetic exchange interactions in [Cr(C6H6)2][TDTD] reveal the presence of 3D interactions, ranging from an antiferromagnetic interaction of -8.96 cm-1 to a ferromagnetic one of 1.70 cm-1. The temperature dependence of the paramagnetic susceptibility χp indicates the dominance of an antiferromagnetic interaction with a negative Weiss constant of -4.8 K and a magnetic ordering at 8 K, which can be characterized in terms of weak ferromagnetism.