Small compound - big colors: synthesis and structural investigation of brightly colored alkaline earth metal 1,3-dimethylviolurates.

A series of brightly colored alkaline earth metal 1,3-dimethylviolurates M(Me2Vio)2 have been prepared and fully characterized. The title compounds AE(Me2Vio)2·nH2O (AE = Mg, n = 6 (3); AE = Ca, n = 8 (4), AE = Sr, n = 6 (5); AE = Ba, n = 4 (6)) were obtained by neutralizing 1,3-dimethylvioluric acid monohydrate (=H(Me2Vio)·H2O; 2) with 0.5 equiv. of the corresponding metal dihydroxides AE(OH)2. The hair-like appearance of the Sr derivative 5 prevented the growth of single-crystals. This problem could be solved by crystallizing the crown ether derivative Sr(Me2Vio)2(18-crown-6) (5a). The isolated salts exhibit intense colors ranging from red to purple. Various attempts to prepare the beryllium derivative Be(Me2Vio)2 failed. Instead, work-up of the reaction mixtures provided pink crystals of a new modification of 2 formulated as [H3O][Me2Vio] (2b) as shown by an X-ray diffraction study. An unexpected oxidation reaction of the barium salt Ba(Me2Vio)2 led to formation of the novel mixed-anion salt Ba(Me2Vio)(Me2NO2Barb)·2H2O (8, Me2NO2Barb- = 1,3-dimethyl-5-nitrobarbiturate anion). Compound 8 could also be synthesized deliberately by treatment of Ba(OH)2 with a 1 : 1 mixture of 2 and 1,3-dimethyl-5-nitrobarbituric acid (7, =H(Me2NO2Barb)·H2O). All new compounds were fully characterized by their IR, Raman, NMR (1H, 13C{1H}) and UV-vis spectra as well as elemental analyses. Single-crystal X-ray diffraction studies revealed that the solid-state structures of compounds 3, 4, 5a and 6 are governed by the typical coordination behavior of the alkaline-earth metals, i.e. increasing coordination numbers and a decreasing degree of hydration when going from Mg to Ba. The dimensions of the structures range from hydrogen-bonded ions (3) over monomeric, neutral complex molecules (4, 5a), to polymeric networks (6). The successful isolation of the mixed-anion barium salt 8 adds a new facet to the coordination chemistry of violurate and related ligands.

Synthesis and Structure of Alkaline Earth Bis{hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate} Complexes: Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba).

The synthesis and structural characterization of Ae(TpiPr2)2 (Ae = Mg, Ca, Sr, Ba; TpiPr2 = hydrido-tris(3,5-diisopropyl-pyrazol-1-yl)borate) are reported. In the crystalline state, the alkaline earth metal centers are six-coordinate, even the small Mg2+ ion, with two κ3-N,N',N''-TpiPr2 ligands, disposed in a bent arrangement (B···Ae···B < 180°). However, contrary to the analogous Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb) compounds, which all exhibit a bent-metallocene structure close to Cs symmetry, the Ae(TpiPr2)2 compounds exhibit a greater structural variation. The smallest Mg(TpiPr2)2 has crystallographically imposed C2 symmetry, requiring both bending and twisting of the two TpiPr2 ligands, while with the similarly sized Ca2+ and Sr2+, the structures are back toward the bent-metallocene Cs symmetry. Despite the structural variations, the B···M···B bending angle follows a linear size-dependence for all divalent metal ions going from Mg2+ to Sm2+, decreasing with increasing metal ion size. The complex of the largest metal ion, Ba2+, forms an almost linear structure, B···Ba···B 167.5°. However, the "linearity" is not due to the compound approaching the linear metallocene-like geometry, but is the result of the pyrazolyl groups significantly tipping toward the metal center, approaching "side-on" coordination. An attempt to rationalize the observed structural variations is made.

Catenated and spirocyclic polychalcogenides from potassium carbonate and elemental chalcogens.

The reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [PPN]Cl (PPN = (Ph3P)2N) produces catena-[S12]2-, the longest structurally characterised polysulfide dianion, or spiro-[Se11]2- as ion-separated [PPN]+ salts.

Bright Photoluminescence of [{(CptBu2 )2 Ce(µ-Cl)}2 ]: A Valuable Technique for the Determination of the Oxidation State of Cerium.

The synthesis and photoluminescence properties of the bright-yellow organocerium complex [{(CptBu2 )2 Ce(µ-Cl)}2 ] (CptBu2 =1,3-di(tert-butyl)cyclopentadienyl) are presented. This coordination compound exhibits highly efficient photoluminescence within the yellow-light wavelength range, with a high internal quantum yield of 61(±2) % at room temperature. The large red shift is attributed to the delocalizing ability of the aromatic ligands, whilst its quantum yield even makes this compound competitive with Ce3+ -activated LED phosphors in terms of its photoluminescence efficiency (disregarding its thermal stability). A bridging connection between two crystallographically independent Ce3+ ions is anticipated to be the reason for the highly efficient photoluminescence, even up to room temperature. The emission spectrum is characterized by two bands in the orange-light range at both 10 K and room temperature, which are attributed to the parity-allowed transitions 5d1 (2 D3/2 )→4f1 (2 F7/2 ) and 5d1 (2 D3/2 )→4f1 (2 F5/2 ) of Ce3+ , respectively. The photoluminescence spectra were interpreted in relation to the structure and vibrational modes of the coordination compound. The spectra and optical properties indicate that trivalent cerium ions are the dominant species in the ground state, which also resolves an often-encountered ambiguity in organocerium compounds. This result shows that photoluminescence spectroscopy is a versatile tool that can help elucidate the oxidation state of Ce in such compounds.

Formation and structural characterization of a europium(II) mono(scorpionate) complex and a sterically crowded pyraza-bole.

The reaction of EuI2(THF)2 with potassium hydro-tris-(3,5-diiso-propyl-pyrazol-yl)borate (K[HB(3,5- iPr2pz)3] (= KTp iPr2, pz = pyrazol-yl) in a molar ratio of 1:1.5 resulted in extensive ligand fragmentation and formation of the europium(II) mono(scorpionate) complex bis-(3,5-diisopropyl-1H-pyrazole)[hydro-tris-(3,5-diiso-propyl-pyrazol-yl)borato]iodido-europium(II), [Eu(C27H46BN6)I(C9H16N2)2] or (Tp iPr2)(3,5- iPr2pzH)2EuIII, 1, in high yield (78%). As a typical by-product, small amounts of the sterically crowded pyraza-bole derivative trans-4,8-bis-(3,5-diiso-propyl-pyrazol-1-yl)-1,3,5,7-tetra-iso-propyl-pyraza-bole, C36H62B2H8 or trans-{(3,5- iPr2pz)HB(µ-3,5- iPr2pz)}2, 2, were formed. Both title compounds have been structurally characterized through single-crystal X-ray diffraction. In 1, two isopropyl groups are each disordered over two orientations with occupancy ratios of 0.574 (10):0.426 (10) and 0.719 (16):0.281 (16). In 2, one isopropyl group is similarly disordered, occupancy ratio 0.649 (9):0.351 (9).

Stabilization of molecular lanthanide polysulfides by bulky scorpionate ligands.

Well-defined lanthanide polysulfide complexes containing S4(2-) and S5(2-) ligands, the samarium(iii) pentasulfide complex Sm(Tp(iPr2))(κ(1)-3,5-(i)Pr2Hpz)(S5) and the tetrasulfide-bridged binuclear ytterbium(iii) complex (µ-S4)[Yb(Tp(iPr2))(κ(1)-3,5-(i)Pr2Hpz)(κ(2)-3,5-(i)Pr2pz)]2 (Tp(iPr2) = hydro-tris(3,5-diisopropylpyrazolyl)borate), have been synthesized and structurally characterized by single-crystal X-ray diffraction.