Synthesis and Stability of Ammonium Selenocyanate [NH4][SeCN] and Its Reactivity toward Ag[SeCN].

[NH4][SeCN] and Ag[SeCN] were synthesized by salt metathesis starting from the respective chlorides and K[SeCN]. Both products were fully characterized by single-crystal and powder X-ray diffraction, differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), and solid-state IR and Raman spectroscopy. Quantum-mechanical calculations allowed for detailed assignment and interpretation of vibrational spectra. For dissolved [NH4][SeCN], nuclear magnetic resonance spectra were collected. High-temperature powder X-ray diffraction (HT-PXRD) allowed for the analysis of the thermal behavior of solid [NH4][SeCN]. Furthermore, the reaction of [NH4][SeCN] with Ag[SeCN] leads to the formation of the ternary salts [NH4][Ag(SeCN)2] and [NH4]3[Ag(SeCN)4]. The structures of the latter were determined from single-crystal X-ray diffraction (SC-XRD) data, and bulk analysis was performed by Rietveld refinement, Raman spectroscopy, and elemental analysis.

The influence of copper on the optical band gap of heterometallic iodido antimonates and bismuthates.

Halogenido metalates of heavy main group elements are versatile semiconductor materials with broad applications. Especially the iodido metalates generally show small optical band gaps, making them suitable for photovoltaics. However, the most promising results have been generated using toxic lead-based materials, raising environmental concerns, while the related and far less toxic bismuth compounds show band gaps too large for direct use in photovoltaics. The introduction of heterometals such as copper can significantly lower the band gap of iodido bismuthates and antimonates, but no clear trend could yet be established in this regard. In this work a short overview over all known copper iodido bismuthates and antimonates is given and this small family of compounds is expanded with nine charged as well as neutral complexes [EkMlIm(P(R)3)n]q- (E = Sb, Bi; M = Cu, Ag; R = Ph, o-tol). The compounds' crystal structures, stability and optical properties are investigated and compared to the findings of quantum chemical investigations. The main excitation is shown to be a copper to antimony or copper to bismuth charge transfer while the relative energetic position of the organic ligand orbitals influences the magnitude of the band gap. This reveals that the nature of the ligands and the coordination environment at the copper atom is crucial for designing new copper iodido antimonates and bismuthates with specific band gaps.

A Comprehensive Study on the Full Series of Alkali-Metal Selenocyanates AI [SeCN] (AI =Li-Cs).

The full series of quasibinary alkali-metal selenocyanates was synthesized either by oxidation of the respective cyanides (A=Li-Rb) or by metathesis (A=Cs). For Li[SeCN] only ball-milling and subsequent annealing led to the isolation of the quasibinary selenocyanate. Their structures were refined from single-crystal and powder X-ray data. The respective solid-state IR and Raman spectra were interpreted with the aid of solid-state quantum-mechanical calculations and DSC-TGA measurements allowed for extraction of melting points. Only for Li[SeCN] a possible phase transition was observed that is discussed on the basis of VT-PXRD experiments. It is also the only quasibinary selenocyanate to form a hydrate (Li[SeCN] ⋅ 2H2 O).

Homoleptic quasilinear metal(i/ii) silylamides of Cr-Co with phenyl and allyl functions - impact of the oxidation state on secondary ligand interactions.

Herein we describe the synthesis and characterization of a variety of new quasilinear metal(i/ii) silylamides of the type [M(N(Dipp)SiR3)2]0,- (M = Cr-Co) with different silyl substituents (SiR3 = SiPh3-nMen (n = 1-3), SiMe2(allyl)). By comparison of the solid state structures we show that in the case of phenyl substituents secondary metal-ligand interactions are suppressed upon reduction of the metal. Introduction of an allyl substituted silylamide gives divalent complexes with additional metal-π-alkene interactions with only weak activation of the C[double bond, length as m-dash]C bond but substantial bending of the principal N-M-N axis. 1e--reduction makes cobalt a more strongly bound alkene substituent, whereas for chromium, reduction and intermolecular dimerisation of the allyl unit are observed. It thus indicates that the general view of low-coordinate 3d-metal ions as electron deficient seems not to apply to anionic metal(i) complexes. Additionally, the obtained cobalt(i) complexes are reacted with an aryl azide giving trigonal imido metal complexes. These can be regarded as rare examples of high-spin imido cobalt compounds from their structural and solution magnetic features.