Farbeffekte in oxidischen and anderen Mn2+-Verbindungen – die Ligandenfeldspektren von MgO/MnO- und CaO/MnO-Mischkristallen sowie von MnAl2O4

Colour Effects in Oxidic and Other Mn²⁺ Compounds – the Ligand Field Spectra of Mixed Crystals MgO/MnO, CaO/MnO, and of MnAl₂O₄ The colour intensity and the shift of the hue is examined for mixed crystals Mg_1?xMn_x^IIO and Mn_1?y^IICa_yO in dependence of the Mn²⁺-concentration and interpreted in terms of Mn²⁺? Mn²⁺ pair interactions and variations of the Mn? O bond length, respectively. The experimental band positions (sextet-quartet transitions) could be fitted quantitatively – also in case of Mn²⁺ in tetrahedral (MnAl₂O₄) and dodecahedral oxygen coordination (Mn₃Al₂Ge₃O₁₂, MnY₂Mg₂Ge₃O₁₂) – by means of crystal field calculations. The obtained ligand field parameters are discussed in comparison with data for octahedral Mn²⁺ ions with H₂O, F^? and Cl^? as ligands.     

Die Kristallstruktur von Perowskiten ANiIIMVIO6. I. Das Sr2[NiTe]O6

The structure of the perovskite compound Sr Ni^IITe^{VI (6)}O₆ (1:1 order in the octahedral sites) is described in detail. The obtained Ni? O distance (2.04 Å a_Te–O = 1.91 Å) together with that one within the corresponding tungsten perovskite (part II) will be analyzed quantitatively with respect to the connection between structure and ligand-field as well as EPR data. The comparison of this distance and the spectroscopic results of the tellurium perovskite with corresponding data of Ni^II-doped MgO however shows already now that an interpretation on the basis of an ionic model is impossible     

Struktur und Bindung in Übergangsmetall-Fluoriden MIIMeIVF6 A. Phasenübergänge

Structure and Bonding in Transitition Metal Fluorides M^IIMe^IVF₆ A. Phase Transitions A summary outline of the structure types of all compounds M^IIMe^IVF₆ known so far is given. Compounds with a 3d transition metal ion in the M^II site crystallize in the cubic ordered ReO₃ lattice and the hexagonal LiSbF₆ structure. For cations with a Jahn- Teller unstable E_g ground state we have found a symmetry reduction to tetragonal and triclinic variants of those two lattice types in addition. Phase transitions between the different structures could be observed by Guinier techniques in the temperature range 80 K < T < 800 K in many cases. The relative stability of the hexagonal low temperature phases in comparison to the cubic high temperature modifications is extensively discussed on the basis of geometric parameters and the electronic properties of the Me^IV and M^II ions. Quite a number of compounds M^IIMe^IVF₆ was prepared and characterized for the first time. The results of the spectroscopic investigation will be published later.     

Farbe und Konstitution bei anorganischen Feststoffen, 11. Mitt.: Die Lichtabsorption des oktaedrisch koordinierten Co2+-Ions in der Mischkristallreihe Mg1−x Co x O und anderen oxidischen Wirtsgittern

Zusammenfassung Für das oktaedrisch koordinierte Co²⁺-Ion werden ein Termschema und Energiegleichungen für zwei charakteristischeDq/B-Werte angegeben und mit deren Hilfe aus den Spektren der Co²⁺-haltigen Ilmenite MgTiO₃ und CdTiO₃ ¹ die Zuordnung des intensitätsstärksten Quartett-Dublett-Überganges ( _a ⁴ T_{1g b} ² T_1g) auf eindeutige Weise ermöglicht.Weiter wird das spektrale Verhalten der Mg_1–x CO _x O-Mischkristalle (0,05x1,0) in Abhängigkeit von der Co²⁺-Konzentration untersucht. Die Änderungen der Bandenintensitäten und desRacah-ParametersB werden wie in der analogen MgO-NiO-Mischkristallreihe² auf Spin-Spin-Wechselwirkungen der über Sauerstoff benachbarten Co²⁺-Ionen zurückgeführt.

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The energy levels of the octahedrally coordinated Co²⁺-ion and energy equations for two characteristicB-values are given, which allow to identify the quartet-doublet-transition ( _a ⁴ T_{1g b} ² T_1g) of the highest intensity from the spectrum of the Co²⁺ containing ilmenites MgTiO₃ and CdTiO₃ ¹.In addition, the variation of the spectra of the Mg_1–x Co _x O-mixed crystals (0.05x1.0) with the Co²⁺ concentration is investigated. The changes in the intensities of the absorption bands and of theRacah-parameterB are (as for the corresponding MgO-NiO-mixed crystals² interpreted as being caused by spin-spin-interactions between Co²⁺ ions bonded to the same oxygen.

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Mit 3 Abbildungen     

Structure and Jahn-Teller effect in mixed crystals Rb2Cr1−xMnxCl4: A single-crystal neutron diffraction study and spectroscopic results

The structures of single crystals Rb₂Cr_1?xMn_xCl₄ (0 ? x ? 1) have been studied by neutron diffraction. A crystal of composition x = 0.01 shows a superstructure of the K₂NiF₄ type [space group Bbcm; a = b = 7.262Å, c = 15.733Å]. The structural refinement [R = 0.043] yields an antiferrodistortive order of tetragonally elongated octahedra (superimposed by a small orthorhombic component) with CrCl bond lengths of 2.43 Å (∥[001]) and 2.40 Å, 2.74 Å (⊥[001]). Structural results for x = 0.01/0.08/0.53/0.63/0.83/0.91/0.97 in space group $\text{I4}\text{mmm}$ [K₂NiF₄ type]—in particular the anomalous ms displacements of Cl(1) in the (001) plane—give evidence that the distortion of the (Mn, Cr)Cl₆ octahedra decreases with increasing x. AOM calculations based on experimental ligand field energies indicate that the individual CrCl₆ polyhedra are more strongly distorted than the (Jahn-Teller stable) MnCl₆ octahedra in mixed crystals with larger x values.     

Geometry and Electronic Structure of CuCl(6)(4-) Polyhedra Doped into (3-Chloroanilinium)(8)[CdCl(6)]Cl(4)-An EPR and Structural Investigation

The EPR single-crystal and powder spectra of mixed crystals of (3-chloroanilinium)(8)(Cd(1-x)Cu(x)Cl(6))Cl(4) are measured as a function of temperature and x and analyzed with respect to the geometry and bonding properties of the CuCl(6) polyhedra. These undergo strong distortions due to vibronic Jahn-Teller coupling, with the resulting tetragonal elongation being superimposed by a considerable orthorhombic symmetry component induced by a host site strain acting as a compression along the crystallographic a axis. This strain becomes apparent in the cadmium compound (x = 0), whose crystal structure is also reported [a = 8.701(2) ?, b = 13.975(2) ?, c = 14.173(2) ?, alpha = 81.62(1) degrees, beta = 72.92(1) degrees, gamma = 77.57(1) degrees, triclinic P&onemacr;, Z = 1]. A calculation of the ground state potential surface and its vibronic structure nicely reproduces the g values, Cu-Cl spacings, and ligand field data. At high copper concentrations (including x = 1), the CuCl(6) polyhedra are coupled elastically, with the long axes of neighboring polyhedra having perpendicular orientations. The elastic correlation presumably is not of the long-range antiferrodistortive type, however. Above about 55 K, the angular Jahn-Teller distortion component becomes dynamically averaged within the time scale of the EPR experiment, leading to local tetragonally compressed CuCl(6) octahedra.     

Photoswitchable Hydrogel Surface Topographies by Polymerisation‐Induced Diffusion

Herein, we describe the preparation of patterned photoresponsive hydrogels by using a facile method. This polymer‐network hydrogel coating consists of N‐isopropylacrylamide (NIPAAM), cross‐linking agent tripropylene glycol diacrylate (TPGDA), and a new photochromic spiropyran monoacrylate. In a pre‐study, a linear NIPAAM copolymer (without TPGDA) that contained the spiropyran dye was synthesised, which showed relatively fast photoswitching behaviour. Subsequently, the photopolymerisation of a similar monomer mixture that included TPGDA afforded freestanding hydrogel polymer networks. The light‐induced isomerisation of protonated merocyanine into neutral spiropyran under slightly acidic conditions resulted in macroscopic changes in the hydrophilicity of the entire polymer film, that is, shrinkage of the hydrogel. The degree of shrinkage could be controlled by changing the chemical composition of the acrylate mixture. After these pre‐studies, a hydrogel film with spatially modulated cross‐link density was fabricated through polymerisation‐induced diffusion, by using a patterned photomask. The resulting smooth patterned hydrogel coating swelled in slightly acidic media and the swelling was higher in the regions with lower cross‐linking densities, thus yielding a corrugated surface. Upon exposure to visible light, the surface topography flattened again, thus showing that a hydrogel coating could be created, the topography of which could be controlled by light irradiation.