Tetrakis-Cyanoacetylides as Building Blocks for a Second Generation of Spin-Switchable Hofmann-type Networks with Enhanced Porosity.

The combination of spin crossover (SCO) with guest incorporation properties has attracted the interest of researchers in the last couple of decades and has led to the design of numerous SCO porous coordination polymers (SCO-PCPs). The most famous class of SCO-PCPs is the Hofmann-type network, which is a very promising material for (chemo)sensing applications. Different strategies have been carried out to expand the classic structure {Fe(pz)[MII(CN)4]} (M = Ni, Pd, Pt) to get larger cavities, but the resulting compounds often showed a poor magnetic behavior. In this work, we present wide-mesh-size spin-switching Hofmann-type networks based on tetrakis-cyanoacetylides synthesized with a newly developed method, resulting in compounds with the general formula {Fe(pz)[M(C3N)4]} (M=Ni, Pd, Pt). The compounds were characterized in their structural, magnetic, and spectroscopic properties. They present 5-fold larger cavities and a drastic increase in porosity. The desired hysteretic and guest-dependent spin-crossover behavior is retained, and in situ chemo-switching of the spin state and the memory effect are also observed.

Identifying the reactive sites of hydrogen peroxide decomposition and hydroxyl radical formation on chrysotile asbestos surfaces.

BACKGROUND: Fibrous chrysotile has been the most commonly applied asbestos mineral in a range of technical applications. However, it is toxic and carcinogenic upon inhalation. The chemical reactivity of chrysotile fiber surfaces contributes to its adverse health effects by catalyzing the formation of highly reactive hydroxyl radicals (HO•) from H2O2. In this Haber-Weiss cycle, Fe on the fiber surface acts as a catalyst: Fe3+ decomposes H2O2 to reductants that reduce surface Fe3+ to Fe2+, which is back-oxidized by H2O2 (Fenton-oxidation) to yield HO•. Chrysotile contains three structural Fe species: ferrous and ferric octahedral Fe and ferric tetrahedral Fe (Fe3+tet). Also, external Fe may adsorb or precipitate onto fiber surfaces. The goal of this study was to identify the Fe species on chrysotile surfaces that catalyze H2O2 decomposition and HO• generation. RESULTS: We demonstrate that at the physiological pH 7.4 Fe3+tet on chrysotile surfaces substantially contributes to H2O2 decomposition and is the key structural Fe species catalyzing HO• generation. After depleting Fe from fiber surfaces, a remnant fiber-related H2O2 decomposition mode was identified, which may involve magnetite impurities, remnant Fe or substituted redox-active transition metals other than Fe. Fe (hydr)oxide precipitates on chrysotile surfaces also contributed to H2O2 decomposition, but were per mole Fe substantially less efficient than surface Fe3+tet. Fe added to chrysotile fibers increased HO• generation only when it became incorporated and tetrahedrally coordinated into vacancy sites in the Si layer. CONCLUSIONS: Our results suggest that at the physiological pH 7.4, oxidative stress caused by chrysotile fibers largely results from radicals produced in the Haber-Weiss cycle that is catalyzed by Fe3+tet. The catalytic role of Fe3+tet in radical generation may also apply to other pathogenic silicates in which Fe3+tet is substituted, e.g. quartz, amphiboles and zeolites. However, even if these pathogenic minerals do not contain Fe, our results suggest that the mere presence of vacancy sites may pose a risk, as incorporation of external Fe into a tetrahedral coordination environment can lead to HO• generation.

The Effect of pH and Biogenic Ligands on the Weathering of Chrysotile Asbestos: The Pivotal Role of Tetrahedral Fe in Dissolution Kinetics and Radical Formation.

Chrysotile asbestos is a soil pollutant in many countries. It is a carcinogenic mineral, partly due to its surface chemistry. In chrysotile, FeII and FeIII substitute Mg octahedra (Fe[6]), and FeIII substitutes Si tetrahedra (Fe[4]). Fe on fiber surfaces can generate hydroxyl radicals (HO. ) in Fenton reactions, which damage biomolecules. To better understand chrysotile weathering in soils, net Mg and Si dissolution rates over the pH range 3.0-11.5 were determined in the presence and absence of biogenic ligands. Also, HO. generation and Fe bulk speciation of pristine and weathered fibers were examined by EPR and Mössbauer spectroscopy. Dissolution rates were increased by ligands and inversely related to pH with complete inhibition at cement pH (11.5). Surface-exposed Mg layers readily dissolved at low pH, but only after days at neutral pH. On longer timescales, the slow dissolution of Si layers became rate-determining. In the absence of ligands, Fe[6] precipitated as Fenton-inactive Fe phases, whereas Fe[4] (7 % of bulk Fe) remained redox-active throughout two-week experiments and at pH 7.5 generated 50±10 % of the HO. yield of Fe[6] at pristine fiber surfaces. Ligand-promoted dissolution of Fe[4] (and potentially Al[4]) labilized exposed Si layers. This increased Si and Mg dissolution rates and lowered HO. generation to near-background level. It is concluded that Fe[4] surface species control long-term HO. generation and dissolution rates of chrysotile at natural soil pH.

Halogenated Alkyltetrazoles for the Rational Design of FeII Spin-Crossover Materials: Fine-Tuning of the Ligand Size.

1-(3-Halopropyl)-1H-tetrazoles and their corresponding FeII spin-crossover complexes have been investigated in a combined experimental and theoretical study. Halogen substitution was found to positively influence the spin transition, shifting the transition temperature about 70 K towards room temperature. Halogens located at the ω position were found to be too far away from the coordinating tetrazole moiety to have an electronic impact on the spin transition. The subtle variation of the steric demand of the ligand in a highly comparable series was found to have a comparatively large impact on the spin-transition behavior, which highlights the sensitivity of the effect to subtle structural changes.

A Modified Synthetic Pathway for the Synthesis of so far Inaccessible N1-Functionalized Tetrazole Ligands - Synthesis and Characterization of the 1D Chain-Type Spin Crossover Compound [Fe(3ditz)3](BF4)2.

A modified phase-transfer-catalyst-assisted synthetic pathway was developed that widens the pool of accessible 1-substituted tetrazoles, which are possible ligands for iron(II) spin-crossover compounds. Within the family of α,ω-bis(tetrazol-1-yl)alkanes, a series of ligands and their respective iron(II) spin-crossover compounds were synthesized and structurally and spectroscopically characterized in the past. The classical route to prepare these ligands is based on the respective amino-precursors. Hence the pool of accessible compounds is limited by the commercial or synthetical availability of α,ω-diaminoalkanes. Furthermore, the concomitant transformation to the tetrazole moieties turns out to be easier for diamino-alkanes with an even number of carbon atoms than for those with an odd number. In line with this observation, the shortest odd-numbered homologues such as 1,1-bis(tetrazol-1-yl)methane (1ditz) and 1,3-bis(tetrazol-1-yl)propane (3ditz) were inaccessible so far. In this paper, we report the successful preparation and characterisation of the classically inaccessible 1,3-bis(tetrazol-1-yl)propane (3ditz) and of its spin-crossover complex [Fe(3ditz)3](BF4)2, which features an abrupt and almost complete spin transition at T[Formula: see text] = 159 K. The single-crystal X-ray structure of the low-spin and the high-spin species is presented. The magnetic data are supported by variable-temperature IR, UV/Vis/NIR, and 57Fe Mössbauer spectra.

Site occupancy and lattice parameters in sigma-phase Co-Cr alloys.

Neutron powder diffraction was used to study the distribution of Co and Cr atoms over different lattice sites as well as the lattice parameters of sigma-phase compounds Co(100 - x)Cr(x) with x = 57.0, 62.7 and 65.8. From the diffractograms recorded in the temperature range of 4.2-300 K it was found for the five crystallographically independent sites that A (2a) and D (8i) are predominantly occupied by Co atoms, while sites B (4f), C (8i) and E (8j) mainly accommodate Cr atoms. The lattice parameters a and c exhibit linear temperature dependencies, with different expansion coefficients in the temperature ranges of 4.2-100 and 100-300 K.

Bifunctional Fe(II) spin crossover-complexes based on ω-(1H-tetrazol-1-yl) carboxylic acids.

To increase the supramolecular cooperativity in Fe(ii) spin crossover materials based on N1-substituted tetrazoles, a series of ω-(1H-tetrazol-1-yl) carboxylic acids with chain-lengths of C2-C4 were synthesized. Structural characterization confirmed the formation of a strong hydrogen-bond network, responsible for enhanced cooperativity in the materials and thus largely complete spin-state transitions for the ligands with chain lenghts of C2 and C4. To complement the structural and magnetic investigation, electronic spectroscopy was used to investigate the spin-state transition. An initial attempt to utilize the bifunctional coordination ability of the ω-(1H-tetrazol-1-yl) carboxylic acids for preparation of mixed-metallic 3d-4f coordination polymers resulted in a novel one-dimensional gadolinium-oxo chain system with the ω-(1H-tetrazol-1-yl) carboxylic acid acting as µ2-η2:η1 chelating-bridging ligand.

Magnetic Characteristics of Ni-Filled Luminescent Porous Silicon.

The aim of the presented work is to combine luminescent porous silicon (PSi) with a ferromagnetic metal (Ni) to modify on the one hand the photoluminescence by the presence of metal deposits and on the other hand to influence the optical properties by an external magnetic field. The optical properties are investigated especially with respect to the wavelength-shift of the photoluminescence due to the metal filling. With increasing metal deposits within PSi the photoluminescence peak is blue-shifted and furthermore an increase of the intensity is observed. Photoluminescence spectra of bare PSi show a maximum around 620 nm whereas in the case of Ni filled samples the peak is blue-shifted to around 580 nm for a deposition time of 15 min. Field dependent magnetic measurements performed with an applied field parallel and perpendicular to the surface, respectively, show a magnetic anisotropy which is in agreement with a thin film. This film-like behavior is caused by the interconnected Ni structures due to the branched porous silicon morphology. The coercivity increases with increasing metal deposition from about 150 Oe to about 450 Oe and also the magnetic anisotropy is enhanced with the growth of metal deposits. Within this work the influence of the magnetic metal filling on the optical properties and the magnetic characterization of the nanocomposites are discussed. The presented systems give not only rise to optoelectronics applications but also to magneto optical integrated devices.

Cooperativity in spin crossover materials as ligand's responsibility - investigations of the Fe(ii) - 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane system.

Criteria for a technologically relevant spin crossover (SCO) material include temperature and abruptness. A series of Fe(ii) - 1,3-bis((1H-tetrazol-1-yl)methyl)bicyclo[1.1.1]pentane SCO complexes with various anions (BF4-, ClO4-, and PF6-) designed using a structure-property based concept is reported. All complexes feature abrupt SCO-behavior with T1/2 between 170 K and 187 K. These materials demonstrate that without stabilizing the effects of incorporated solvents or a hydrogen bond-network, the observed cooperativity during high-spin-low-spin transition is anion independent and originates only from the rigidity and internal strain of the propellane-moiety in the ligand. Spectroscopy and structural investigations of these materials are supported by quantum chemical calculations.

Ternary borides Nb7Fe3B8 and Ta7Fe3B8 with Kagome-type iron framework.

Two new ternary borides TM7Fe3B8 (TM = Nb, Ta) were synthesized by high-temperature thermal treatment of samples obtained by arc-melting. This new type of structure with space group P6/mmm, comprises TM slabs containing isolated planar hexagonal [B6] rings and iron centered TM columns in a Kagome type of arrangement. Chemical bonding analysis in Nb7Fe3B8 by means of the electron localizability approach reveals two-center interactions forming the Kagome net of Fe and embedded B, while weaker multicenter bonding present between this net and Nb atoms. Magnetic susceptibility measurements reveal antiferromagnetic order below TN = 240 K for Nb7Fe3B8 and TN = 265 K for Ta7Fe3B8. Small remnant magnetization below 0.01µB per f.u. is observed in the antiferromagnetic state. The bulk nature of the magnetic transistions was confirmed by the hyperfine splitting of the Mössbauer spectra, the sizable anomalies in the specific heat capacity, and the kinks in the resistivity curves. The high-field paramagnetic susceptibilities fitted by the Curie-Weiss law show effective paramagnetic moments µeff≈ 3.1µB/Fe in both compounds. The temperature dependence of the electrical resistivity also reveals metallic character of both compounds. Density functional calculations corroborate the metallic behaviour of both compounds and demonstrate the formation of a sizable local magnetic moment on the Fe-sites. They indicate the presence of both antiferro- and ferrromagnetic interactions.

Magnetic properties of superparamagnetic nanoparticles loaded into silicon nanotubes.

In this work, the magnetic properties of silicon nanotubes (SiNTs) filled with Fe3O4 nanoparticles (NPs) are investigated. SiNTs with different wall thicknesses of 10 and 70 nm and an inner diameter of approximately 50 nm are prepared and filled with superparamagnetic iron oxide nanoparticles of 4 and 10 nm in diameter. The infiltration process of the NPs into the tubes and dependence on the wall-thickness is described. Furthermore, data from magnetization measurements of the nanocomposite systems are analyzed in terms of iron oxide nanoparticle size dependence. Such biocompatible nanocomposites have potential merit in the field of magnetically guided drug delivery vehicles. PACS: 61.46.Fg; 62.23.Pq; 75.75.-c; 75.20.-g.

Magnetic interactions between metal nanostructures within porous silicon.

Electrochemically deposited magnetic nanostructures arranged in a three-dimensional system are investigated with respect to their cross-talk between each other. The nanostructures are embedded in porous silicon templates with different morphologies which means pores offering dendritic growth of different strengths. An increase of the uniformity of the pores is concomitant with an increase of the smoothness of the metal deposits which strongly influences the magnetic behavior of the system. Less dendritic structures lead to an increase of the coercivity of the nanocomposite which reveals less cross-talk between the metal deposits due to a modification of the stray fields. The system allows in a cheap and simple way to tune the magnetic interactions of magnetic nanostructures in a three-dimensional arrangement. PACS: 81.05.Rm; 81.07.Gf; 75.75.-c.

Variable blocking temperature of a porous silicon/Fe3O4 composite due to different interactions of the magnetic nanoparticles.

In the frame of this work, the aim was to create a superparamagnetic nanocomposite system with a maximized magnetic moment when magnetized by an external field and a blocking temperature far below room temperature. For this purpose, iron oxide nanoparticles of 3.8-, 5- and 8-nm size have been infiltrated into the pores of porous silicon. To fabricate tailored magnetic properties of the system, the particle size and the magnetic interactions among the particles play a crucial role. Different concentrations of the particles dispersed in hexane have been used for the infiltration to vary the blocking temperature TB, which indicates the transition between the superparamagnetic behavior and blocked state. TB is not only dependent on the particle size but also on the magnetic interactions between them, which can be varied by the particle-particle distance. Thus, a modification of the pore loading on the one hand and of the porous silicon morphology on the other hand results in a composite material with a desired blocking temperature. Because both materials, the mesoporous silicon matrices as well as the Fe3O4 nanoparticles, offer low toxicity, the system is a promising candidate for biomedical applications.

Porous silicon/Ni composites of high coercivity due to magnetic field-assisted etching.

Ferromagnetic nanostructures have been electrodeposited within the pores of porous silicon templates with average pore diameters between 25 and 60 nm. In this diameter regime, the pore formation in general is accompanied by dendritic growth resulting in rough pore walls, which involves metal deposits also offering a branched structure. These side branches influence the magnetic properties of the composite system not only due to modified and peculiar stray fields but also because of a reduced interpore spacing by the approaching of adjacent side pores. To improve the morphology of the porous silicon structures, a magnetic field up to 8 T has been applied during the formation process. The magnetic field etching results in smaller pore diameters with less dendritic side pores. Deposition of a ferromagnetic metal within these templates leads to less branched nanostructures and, thus, to an enhancement of the coercivity of the system and also to a significantly increased magnetic anisotropy. So magnetic field-assisted etching is an appropriate tool to improve the structure of the template concerning the decrease of the dendritic pore growth and to advance the magnetic properties of the composite material.

Neutron powder diffraction with (nat)Sm: crystal structures and magnetism of a binary samarium deuteride and a ternary samarium magnesium deuteride.

Binary SmH(3) (trigonal, a=656.7(3), c=680.1(3) pm, P$\bar 3$c1, Z=6), ternary SmMg2H7 (tetragonal, a=626.47(6), c=937.2(2) pm, P4(1)2(1)2, Z=4) and the corresponding deuterides SmD3 (a=653.9(1)m, c=676.7(2) pm) and SmMg2D7 (a=624.10(1), c=934.81(2) pm) have been prepared by hydrogenation (deuteration) of elemental samarium and the Laves phase SmMg2, respectively, and investigated by X-ray and neutron powder diffraction and SQUID and vibration magnetometry. The problem of the enormous neutron absorption of the natural isotopic mixture (natSm) is circumvented by carefully choosing the neutron wavelength (approximately 50 pm) and the use of double-walled cylindrical sample holders and a high-intensity neutron diffractometer (D4c at ILL). SmD3 crystallises with a tysonite-type structure and has three independently ordered deuterium atom sites with trigonal-planar, trigonal-pyramidal and tetrahedral metal environments and Sm--D bond lengths in the range 220(1)-258(1) pm (average: 235 pm). SmMg2D7 is a new deuteride that crystallises with an LaMg2D7-type structure. It displays four fully occupied deuterium sites having triangular and tetrahedral metal environments and Sm--D bond lengths in the range 227.6(5)-246.8(8) pm (average: 239 pm). These are the first samarium-deuterium bond lengths to be reported. Both deuterides are paramagnetic down to 2 K (SmD3: mueff=0.63(1) muB, thetap approximately -4 K; SmMg2D7: mueff=0.57(2) muB, thetap approximately -4 K). Their crystal structures and chemical and physical properties suggest mainly ionic bonding according to the limiting ionic formulae Sm3+(H-)3 and Sm3+(Mg2+)2(H-)7.

[Fe(mu-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour.

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(mu-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T(1/2) / =136 K and T(1/2) / =133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4* counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(mu-btzmp)2(btzmp)2](ClO4)2.