Thermal deprotonation and condensation of melamine in the presence of indium(III)chloride.

The thermal condensation of melamine into molecules melam, melem, and the one-dimensional polymer melon has already been reported. An interesting question arises about the impact of other compounds being present in this process of thermal conversion. The solid-state reaction of C3N6H6 with InCl3 leads to a novel compound featuring deprotonated melam units in a supramolecular assembly, based on the [C12N20H8]4- anion that is interconnected in the structure via N-In-N bonding. The reaction pathway of the formation of this compound is investigated by thermal analysis and the crystal structure of unique (NH4)[(InCl2)3(C12N20H8)]·â…”[InCl3(NH3)] is reported as well as its photoluminescence properties.

Electronic structure and transport in the potential Luttinger liquids CsNb3Br7S and RbNb3Br7S.

The crystal structures of ANb3Br7S (A = Rb and Cs) have been refined by single crystal X-ray diffraction, and are found to form highly anisotropic materials based on chains of the triangular Nb3 cluster core. The Nb3 cluster core contains seven valence electrons, six of them being assigned to Nb-Nb bonds within the Nb3 triangle and one unpaired d electron. The presence of this surplus electron gives rise to the formation of correlated electronic states. The connectivity in the structures is represented by one-dimensional [Nb3Br7S]- chains, containing a sulphur atom capping one face (µ3) of the triangular niobium cluster, which is believed to induce an important electronic feature. Several types of studies are undertaken to obtain deeper insight into the understanding of this unusual material: the crystal structure, morphology and elastic properties are analysed, as well the (photo-)electrical properties and NMR relaxation. Electronic structure (DFT) calculations are performed in order to understand the electronic structure and transport in these compounds, and, based on the experimental and theoretical results, we propose that the electronic interactions along the Nb chains are sufficiently one-dimensional to give rise to Luttinger liquid (rather than Fermi liquid) behaviour of the metallic electrons.

The luminescent semiconductor Pb7I6(CN2)4.

The development of new compounds in the domain of metal dinitridocarbonates is most efficiently performed via solid-state metathesis or simply by addition reactions. Our discovery of Pb7I6(CN2)4 is the result of a solid-state reaction of PbCN2 with PbI2 at 420 °C. Its crystal structure was solved and refined from X-ray diffraction data based on a single crystal with the space group P63/mmc. The crystal structure is based on a network of lead tetrahedra, lead trigonal bipyramids and lead octahedra interconnected by [NCN]2- and iodide. Properties of the material were investigated by diffuse reflection measurement, photoluminescence measurements, and electronic band structure calculations demonstrating that this material is a semiconductor.

Tungsten Iodide Clusters as Singlet Oxygen Photosensitizers: Exploring the Domain of Resonant Energy Transfer at 1 eV.

The photophysics of selected tungsten iodide clusters was examined with respect to their role as a photosensitizer for the production of singlet oxygen, O2(a1Δg). We examined all-iodo octahedral clusters, [W6I8(I6)]2-, and ligand-substituted octahedral clusters, [W6I8(L6)]2-, in which the ligand, L, occupies the outer apical positions surrounding the cluster core. We also examined a square-pyramidal cluster, [W5I8(I5)]-, in which the tungsten core was presumably more accessible to diffusional encounter with ground state oxygen, O2(X3Σg-). For the compounds examined, we find pronounced cluster-dependent changes in the yield of photosensitized O2(a1Δg) production. In particular, although the iodine-encased octahedral cluster, [W6I8(I6)]2-, is an efficient O2(a1Δg) sensitizer, the pyramidal cluster, [W5I8(I5)]-, does not make O2(a1Δg) at all. The latter provides fundamental insight into the important case where the sensitizer triplet state is nearly degenerate with the O2(X3Σg-)-O2(a1Δg) transition energy at 1 eV. Our data indicate that even with near resonance, energy transfer to form O2(a1Δg) will not occur within the 3sensitizer-O2(X3Σg-) encounter pair if other more efficient channels for energy dissipation are available.

Up-conversion white emission and other luminescence properties of a YAG:Yb2O3·Tm2O3·Ho2O3@SiO2 glass-nanocomposite.

We report on a glass-nanocomposite material consisting of yttrium aluminum garnet (Y3Al5O12, YAG) nanocrystals co-doped with Yb3+, Tm3+ and Ho3+ ions as well as entrapped into a SiO2 xerogel. This 94YAG·5Yb2O3·0.8Tm2O3·0.2Ho2O3@SiO2 (abbr. YAG:YbTmHo@SiO2) nanocomposite material has been prepared by sol-gel procedure. Its structure and morphology has been characterized by means of X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques as well as energy dispersive X-ray (EDX), X-ray photoelectron (XPS) and luminescence spectroscopies. The luminescent glass-nanocomposite exhibited an up-conversion effect under λ exc = 980 nm and emission when excited under 355 nm in steady-state conditions. Then time-resolved luminescence emission was observed, when the sample was excited at 290 and 355 nm by a pulse laser. Average decay times for the SiO2 matrix and for some transitions of the Tm3+ and Ho3+ dopants present in the YAG:YbTmHo@SiO2 material have been evaluated. The luminescent nanocomposite when excited under 290 or 355 nm wavelengths in both conditions emits blue light. However, the nanocomposite is promising as a single-source white-light phosphor owing to its up-conversion luminescence under 980 nm excitation. Such optical features make the studied material an alternative phosphor.

A journey through ternary lead chlorido tungstates by thermal scanning.

The reduction of tungsten hexachloride with lead powder was investigated by differential scanning calorimetry (DSC) combined with X-ray diffraction (XRD) studies. Intermediate compounds along the way of the reduction of W6+ to W2+ were detected, prepared by solid-state synthesis, and structurally characterized by X-ray diffraction techniques. Five new compounds, namely Pb0.5WCl6, PbW2Cl10, Pb1.5[W3Cl13], Pb2Cl[W3Cl13], and Pb[W6Cl14] are discovered to be formed with increasing temperature, and structurally characterized within this study. The analysis of the reduction pathway is meant to gain a better understanding of the metallothermic reduction process and intercalation chemistry in the solid state.

Facile Way of Synthesis for Molybdenum Iodides.

Molybdenum iodides are prepared based on a new way of synthesis, namely, via reductive metathesis reaction of MoCl5 with SiI4. MoI3 was formed at 150 °C. Mo6I12 and the new molybdenum iodides Mo6I16 and Mo6I18 with the well-known [Mo6I8]4+ cluster core were obtained in the temperature range 550-600 °C. Compounds were structurally characterized by powder and single-crystal X-ray diffraction techniques.

A ligand substituted tungsten iodide cluster: luminescence vs. singlet oxygen production.

Octahedral tungsten iodide clusters equipped with apical ligands (L) are synthesized to implement substantial photophysical properties. The [W6I8(CF3COO)6]2- cluster reported herein is the first example of a family of ligand substituted [W6I8L6]2- clusters. Such compounds are expected to exhibit a rich photochemistry in which the apical ligands play a crucial role. The versatile solid state and solution phase photophysical properties of (TBA)2[W6I8(CF3COO)6] described herein parallel characteristics obtained in some photophysically active organic compounds, including a broad absorption in the UV/VIS region. Upon irradiation of this compound, a broad red emission is observed in the VIS/NIR region resulting from excited triplet states, and singlet oxygen (a1Δg) is generated in the presence of O2.

A Facile Method for the Synthesis of Binary Tungsten Iodides.

The preparation of tungsten iodides in large quantities is a challenge because these compounds are not accessible using an easy synthesis method. A new, remarkably efficient route is based on a halide exchange reaction between WCl6 and SiI4. The reaction proceeds at moderate temperatures in a closed glass vessel. The new compounds W3I12 (W3I8 ⋅2 I2) and W3I9 (W3I8 ⋅½I2) containing the novel [W3I8] cluster are formed at 120 and 150 °C, and remain stable in air. W3I12 is an excellent starting material for the synthesis of other metal-rich tungsten iodides. At increasing temperature these trinuclear clusters undergo self-reduction until an octahedral tungsten cluster is formed in W6I12 . The synthesis, structure, and an analysis of the bonding of compounds containing this new trinuclear tungsten cluster are presented.

Synthesis and SHG properties of two new cyanurates: Sr3(O3C3N3)2 (SCY) and Eu3(O3C3N3)2 (ECY).

The new cyanurates Sr3(O3C3N3)2 (SCY) and Eu3(O3C3N3)2 (ECY) were prepared via exothermic solid state metathesis reactions from MCl2 (M = Sr, Eu) and K(OCN) in silica tubes at 525 °C. Both structures were characterized by means of powder and single crystal X-ray diffraction, and their structures are shown to crystallize with the noncentrosymmetric space group R3c (No. 161). Infrared spectra and nonlinear optical properties (NLO) of SCY and ECY are reported in comparison to those of CCY and ß-BaB2O4 (ß-BBO).

Synthesis, structure, and frequency-doubling effect of calcium cyanurate.

Calcium cyanurate is synthesized by reacting calcium chloride with potassium cyanate following a solid-state reaction. The formation of the new compound Ca3(O3C3N3)2 (CCY), which occurs by the cyclotrimerization of cyanate ions, was examined thermoanalytically and the crystal structure was determined by single-crystal structure analysis. The structure of CCY is closely related to the structure of the well-known oxoborate ß-BaB2O4 (BBO). Second harmonic generation (SHG) measurements on crystal powders show a higher SHG efficiency for CCY than for BBO by about one order of magnitude.

Structure of a new chloroauric acid.

The new tetrachloroaurate ethanol hydrate HAuCl4·0.65C2H5OH·1.35H2O was prepared from chloroauric acid trihydrate in ethanol. The compound crystallizes in the triclinic space group P \bar 1 (No. 2). The [AuCl4](-) units in the structure have approximately square-planar symmetry, forming chains parallel to the crystallographic b-axis direction.

Solid state complex chemistry: formation, structure, and properties of homoleptic tetracyanamidogermanates RbRE[Ge(CN2)4] (RE = La, Pr, Nd, Gd).

Tetracyanamidometallates with the general formula RbRE[T(CN2)4] (RE = La, Pr, Nd, Gd; T = Si, Ge) were prepared by solid state metathesis reactions starting from stoichiometric mixtures of RECl3, A2[TF6], and Li2(CN2). Reactions were studied by differential thermal analysis that showed ignition temperatures between 360 and 390 °C for the formation of RbGd[T(CN2)4] with T = Si and Ge. The powder diffraction patterns of RbRE[Ge(CN2)4] were indexed isotypically to the already known RbRE[Si(CN2)4] compound. IR spectra of RbLa[Ge(CN2)4] were measured and compared with those of RbLa[Si(CN2)4]. (73)Ge, (87)Rb, and (139)La solid state NMR measurements and density functional theory calculations were used to verify the novel homoleptic [Ge(CN2)4](4-) ion. Luminescence properties of Eu(3+), Ce(3+), and Tb(3+) doped samples are reported.

From cyanate to cyanurate: cyclotrimerization reactions towards the novel family of metal cyanurates.

The novel metal cyanurates LiSr(O3C3N3) and Li3Sr2F(O3C3N3)2 were prepared by exothermic solid state metathesis reactions and characterized by single crystal X-ray diffraction. Crystalline powders were prepared by reactions of alkali earth halides (SrCl2 and SrF2) with Li(OCN) in 1:3 molar ratios, at 450 and 575 °C. The reaction with chloride yielded LiSr(O3C3N3), and the reaction starting from the fluoride yielded LiSr(O3C3N3)·1/2LiF, containing additional LiF in the structure. Both crystal structures revealed the presence of the (O3C3N3)(3-) ions which were formed by cyclotrimerization reaction of (OCN)(-) ions. The reactions were monitored by differential thermal analysis. Infrared spectra of the compounds are reported.

LaSr3F5(CN2)2: a prototype structure for mixed-valent Eu4F5(CN2)2.

The new compound LaSr(3)F(5)(CN(2))(2) was prepared and structurally characterized as a prototype structure for the remarkably distorted mixed-valent compound Eu(4)F(5)(CN(2))(2), which contains four distinct europium ions in the structure: one Eu(3+) and three Eu(2+). Instead of repeating the given distorted structural pattern, LaSr(3)F(5)(CN(2))(2) forms a structure which can be considered as an ideal high-symmetry structure for Eu(4)F(5)(CN(2))(2), due to the occupation of La(3+) and Sr(2+) ions on one and the same crystallographic position. The crystal symmetry of this structure is an interesting issue to compare with what has been previously proposed.

Solid state synthesis of homoleptic tetracyanamidoaluminates.

Tetracyanamidoaluminates of the type LiM(2)[Al(CN(2))(4)] with M = Eu and Sr were prepared by solid-state metathesis reactions departing from EuF(2) (or SrF(2)), AlF(3), and Li(2)(CN(2)) in a 2 : 1 : 4 molar ratio. The ignition temperature of the exothermic formation of LiSr(2)[Al(CN(2))(4)] was obtained near 420 °C. An X-ray single-crystal structure refinement performed for LiEu(2)[Al(CN(2))(4)] revealed the presence of the novel homoleptic [Al(CN(2))(4)](5-) ion in the structure. The X-ray powder diffraction pattern of LiSr(2)[Al(CN(2))(4)] was indexed isotypically.

Refined crystal structure and idealized structure of mixed-valent Eu4F5(CN2)2: transition possible.

The new europium fluoride carbodiimide Eu(4)F(5)(CN(2))(2) was synthesized by solid state reaction from mixtures of EuF(3) and Li(2)(CN(2)) at 700 °C. The crystal structure as refined by single crystal X-ray diffraction (P ̅42(1)c, no. 114, a = 16.053(1) Å, c = 6.5150(6) Å, Z = 8) reveals three crystallographically distinct [N═C═N](2-) ions in the structure of mixed-valent Eu(4)F(5)(CN(2))(2). The presence of one Eu(3+) and three Eu(2+) per formula unit Eu(4)F(5)(CN(2))(2) is confirmed by magnetic measurements and (151)Eu-Mössbauer spectroscopy. The arrangement of Eu ions and gravity centers of [NCN](2-) ions in the structure of Eu(4)F(5)(CN(2))(2) follow the motif formed by atoms in the CuAl(2)-type structure. A possible high-symmetry structure of Eu(4)F(5)(CN(2))(2) is discussed on the basis of a group-subgroup scheme.

Synthesis of the guaianolide ring system via cycloaddition of a bicyclic carbonyl ylide with allyl propiolate.

A cyclic carbonyl ylide with a trans-annulated cyclopentane ring was generated by a Rh(2)(OAc)(4)-catalyzed reaction from a diazoketone precursor and trapped with allyl propiolate. The 1,3-dipolar cycloaddition led to the stereoselective formation of an oxygen-bridged polycycle. Via Curtius degradation, the cycloadduct was transformed to the ring skeleton typical of the sesquiterpene family of guaianolides.

The trigonal prismatic cluster compound W6CCl15 and a carambolage of tungsten clusters in the structure of the heteroleptic cluster compound W30C2(Cl,Br)68.

Reactions between W(6)Cl(12) and carbon halides can initiate a cascade of reactions and reaction products, yielding W(6)Cl(18), W(6)CCl(18), and W(6)CCl(15) with increasing temperature, before decomposition into tungsten carbide is obtained. The new compound W(6)CCl(15) and the new heteroleptic compound W(30)C(2)(Cl,Br)(68) obtained from these reactions were structurally characterized. The structure of W(30)C(2)X(68) combines a carambolage of two distinct octahedral and one centered trigonal prismatic cluster in one structure as refined by X-ray single-crystal diffraction (P1, Z = 1; a = 12.003(2) A, b = 14.862(3) A, c = 15.792(3) A, alpha = 88.75(2) degrees, beta = 68.85(2) degrees, gamma = 71.19(2) degrees). The unit cell content W(30)C(2)X(68) accommodates five hexanuclear tungsten clusters, similar by a total of three octahedral [W(6)X(8)] type clusters and two carbon-centered trigonal prismatic [W(6)CX(12)] type clusters, sharing terminal halogen atoms to form a network structure. The trigonal prismatic cluster compound W(6)CCl(15) (P2(1)/c, Z = 4; a = 9.8830(4) A, b = 11.8945(4) A, c = 17.8670(7) A, beta = 107.883(2) degrees) is related to the already known compound W(6)CCl(16). According to X-ray powder structure refinement, the structure is showing a special connectivity pattern with short intercluster W-W contacts between trigonal prismatic cluster units.

Solid state metathesis reactions as a conceptual tool in the synthesis of new materials.

Solid state metathesis reactions can be used in the syntheses of inorganic solids and for strategic design of novel, eventually thermally labile materials. An explorative study of solid state metathesis reactions is presented for a number of examples, including syntheses of nitridoborates, carbodiimides, tetracyanoborates, tetracyanamidosilicates, carbon-nitride materials, and a number of other exciting compounds. This unique type of reaction is very efficient because it uses the intrinsic energy of reaction partners being involved. Desired compositions are achieved by appropriate starting materials and their relative amounts being combined into a solid state metathesis reaction. Reactions can be controlled through the heating-up procedure and by using a reactive flux, which may lower the ignition temperature of a reaction mixture and promote crystal growth of products.