Selective synthesis of triangular cluster oxido-sulfidocomplexes of Mo and W: High yield preparations of [Mo3O2S2(H2O)9], [W3O2S2(H2O)9], [W2MoO2S2(H2O)9] and their derivatization

Reaction of [Mo₂O₂(μ-S)₂(H₂O)₆]²⁺ with Mo(CO)₆ or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo₃(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (1). Similarly, [W₃(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (2) is obtained from [W₂O₂(μ-S)₂(H₂O)₆]²⁺ and W(CO)₆. While reaction of [Mo₂O₂(μ-S)₂(H₂O)₆]²⁺ with W(CO)₆ mainly proceeds as simple reduction to give 1, [W₂O₂(μ-S)₂(H₂O)₆]²⁺ with Mo(CO)₆ produces new mixed-metal cluster [W₂Mo(μ₃-S)(μ-O)₂(μ-S)(H₂O)₉]⁴⁺ (3) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo₃O₂S₂(H₂O)₆Cl₃]₂CB[6]}Cl₂⋅18H₂O (4) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M₃O₂S₂(acac)₃(py)₃]PF₆ (M₃ = Mo₃, W₃, W₂Mo; 5a-c), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and ¹H NMR spectroscopy. Crystal structure of (H₅O₂)(Me₄N)₄[W₃(μ₃-S)(μ₂-S)(μ₂-O)₂(NCS)₉] (6), obtained from 2, is also reported.     

A novel large heteropolytungstate constructed from two types of lacunary Keggin anions: K7Na13[(PW11O39)2(PW9O34)2(W2O3)2] · 25H2O

A novel crown-shaped heteropolytungstate is formed by covalently linking two [PW₁₁O₃₉]⁷⁻ and two [PW₉O₃₄]⁹⁻ fragments with four WO₆ octahedra, which represents not only the largest tungstophosphate constructed from two types of building blocks without considering the 4f lanthanide or other 3d transition metal ion linkers but also the highest degree of aggregation known in the large clusters incorporating monovacant lacunary anions.     

Preparation and structure of [Ru2(O2CMe)4]2[Fe(CN)5NO] and magnetically ordered Hx[Ru2(O2CMe)4]3−x[Cr(CN)5NO] possessing interpenetrating lattices

Reaction of [Ru₂(O₂CMe)₄]Cl with K₃[Cr(CN)₅NO] in water forms H_x[Ru^II/III₂(O₂CMe)₄]_3−x-[Cr(CN)₅NO]·zH₂O (x = 0.2) that magnetically orders at 4.0 K and possesses an interpenetrating body centered cubic [a = 13.2509(2) Å] structure with random locations of the bridging nitrosyl ligands, and x/3 vacant cation sites. Similarly, the aqueous reaction of [Ru₂(O₂CMe)₄]Cl with Na₂[Fe(CN)₅NO] forms paramagnetic [Ru₂(O₂CMe)₄]₂[Fe(CN)₅NO]·H₂O, which has a similar tetragonal interpenetrating structure [a = 13.0186(1) Å, c = 13.0699(2) Å] where the NO ligands are presumably nonbridging and 1/3 of the expected cation sites are unoccupied. The presence of uncoordinated NO sites in addition to missing neighboring [Ru₂(O₂CMe)₄]⁺ units, results in significant vacancies (or holes) in the lattice.     

Synthesis and optical study of Ln(III)(tetramethylurea)(AsF6)3 (Ln = LaLu,Y) and crystal structure for Ln = Eu [Eu(TMU)6(AsF6)3]

The fluorescence spectrum of Eu³⁺ recorded at a temperature of 12 K between 14.000 and 20.000 cm^?1 shows transitions from the excited stare ⁵D_o to the Stark components of the lowest ⁷F_j. The optical analysis suggests an octahedral site symmetry for the rare earth ion which is confirmed by the three-dimensional crystal determination. The highly disordered crystal structure refined in space group F23 to an R-factor of 13.2%. Both the europium and the arsenic ions are located in special positions of point symmetry 23(T). The EuO bond distance is 2.28 Å. The value of the B_q^k parameters was determined.     

Synthesis and luminescent properties of lanthanide homoleptic mercaptothi(ox)azolate complexes: Molecular structure of Ln(mbt)3 (Ln = Eu, Er)

The thiolate complexes of rare earth metals Ln(SR)₃ (La, HSR = 2-mercaptothiazoline (1); La, HSR = 2-mercaptobenzoxazole (2); Y, La, Sm, Eu, Tb, Gd, Er, Tm, HSR = 2-mercaptobenzothiazole (3)) were synthesized in 84-97% yield by the reactions of silylamides Ln[N(SiMe₃)₂]₃ with respective thiols. The products were characterized by elemental analysis, IR and UV/Vis spectroscopy. The structures of 3(Eu) and 3(Er) were determined by single-crystal X-ray diffraction. All obtained compounds revealed efficient luminescence in the region 400-550 nm at 293 K assigned to the ligands emission. Besides, the luminescent spectra of thiolates 3 at 77 K displayed the phosphorescent band of the ligand at 550 nm and in the cases of 3(Eu) and 3(Tb) the sets of emissions bands characteristic for Eu³⁺ and Tb³⁺ ions.     

Preparation and characterization of the layered borophosphates M(H2O)2[B2P2O8(OH)2]·H2O (M = Fe, Co, Ni)

The isotypic layered transition metal borophosphates M^II(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O (M^II = Fe, Co, Ni) were prepared under hydrothermal conditions. Their crystal structures were determined by single-crystal X-ray diffraction data and revealed an isotypic relationship to Mg(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O, a structure containing wavy 6³ nets formed by tetrahedral phosphate and hydrogenborate groups interconnected in an alternating fashion by sharing common apices. The crystalline compounds were also characterized by chemical analyses, scanning electron microscopy, energy dispersive X-ray analyses, thermal analyses, IR-spectroscopy and magnetic susceptibility measurements.     

Rb2[B12(OH)12]·2H2O and Rb2[B12(OH)12]·2H2O2: Hydrate and perhydrolate of rubidium dodecahydroxo-closo-dodecaborate

The orthorhombically crystallizing salts Rb₂[B₁₂(OH)₁₂]·2H₂O (a = 1576.81(9), b = 813.08(5), c = 1245.32(7) pm) and Rb₂[B₁₂(OH)₁₂]·2H₂O₂ (a = 1616.54(9), b = 814.29(5), c = 1260.12(7) pm) could be prepared from Rb₂[B₁₂H₁₂] and hydrogen peroxide. Both crystal structures were determined by X-ray single crystal diffraction and refined in the space group Cmce. They are not isostructural to the other compounds containing icosahedral dodecahydroxo-closo-dodecaborate dianions [B₁₂(OH)₁₂]²⁻ and potassium, rubidium or cesium cations already known to literature, but both title compounds crystallize quasi-isotypically exhibiting Rb⁺ cations in 10-fold oxygen coordination. The hydrogen peroxide adduct (Rb₂[B₁₂(OH)₁₂]·2H₂O₂) is explosive on shock and heat, while the hydrate (Rb₂[B₁₂(OH)₁₂]·2H₂O) is not.     

Hydrothermal synthesis and structure of [Ni(tpyrpyz)2]2[Mo4O12F2][Mo6O19] · 2H2O, a material exhibiting an unusual tetranuclear polyoxofluoromolybdate cluster [Mo4O12F2]

The hydrothermal reaction of a solution of Ni(CH₃CO₂)₂ · 4H₂O, MoO₃, tetra-4-pyridylpyrazine, H₂O₃PCH₃, and HF at 200 °C for 96 h yields orange crystals of [Ni(tpyrpyz)₂]₂[Mo₄O₁₂F₂][Mo₆O₁₇] · 2H₂O (1 · 2H₂O). The structure consists of discrete {Ni(tpyrpyz)₂}²⁺ cations and {Mo₆O₁₉}²⁻ and {Mo₄O₁₂F₂}²⁻ anionic clusters. The hexamolybdate is the well-documented octahedron of octahedra, that is, six {MoO₆} octahedra in a compact edge-sharing arrangement. The novel oxyfluoride cluster {Mo₄O₁₂F₂}²⁻ features two {MoO₄F₂} octahedra, sharing the edge defined by the fluoride ligands; the octahedral Mo sites corner-share to two {MoO₄} tetrahedra in the μ₂-O, O^′ bridging mode.     

Layered (2-D) structure of [Ru2(O2CMe)4]2[Ni(CN)4] determined via Rietveld refinement of synchrotron powder diffraction data

Reaction of [Ru₂(O₂CMe)₄]Cl and K₂[Ni(CN)₄] forms [Ru₂(O₂CMe)₄]₂[Ni(CN)₄] with the targeted layered structure possessing Ru-NCNi linkages, albeit strained, with Ru-NC and Ni-CN angles in the range of 147-167°. The magnetic properties of [Ru₂(O₂CMe)₄]₂[Ni(CN)₄] can be fit to a zero-field splitting model with D/k_B = 95 K (66 cm⁻¹).     

Geometrical isomers of bis(benzimidazol-2-ylethyl)sulfide)cobalt(II) diperchlorates: synthesis, structure, spectra and redox behavior of pink-[Co(bbes)2](ClO4)2 and blue-[Co(bbes)2](ClO4)2

1:1 and 1:2 cobalt complexes of bis(benzimidazol-2-ylmethyl)amine (bbma) bis(benzimidazol-2-ylmethyl)sulfide (bbms), bis(benzimidazol-2-ylethyl)sulfide (bbes) and diethylenetriamine (dien) were prepared and their spectral and redox behavior studied. Two geometrical isomers pink-[Co(bbes)₂]²⁺ and blue-[Co(bbes)₂]²⁺ were obtained when the complexes were prepared by using with bbes and they were separated manually and recrystallized. The octahedral structure of pink-[Co(bbes)₂]²⁺ was resolved by X-ray analysis. The electronic spectra show the presence of two geometrical isomers for Co(bbes)₂²⁺ in the solid state; for example, the spectral bands of pink-[Co(bbes)₂]²⁺ differs markedly with those of blue-[Co(bbes)₂]²⁺. This is consistent with the results obtained from magnetic measurements (5.10 BM for pink-Co(bbes)₂²⁺ and 4.72 BM for blue-[Co(bbes)₂]²⁺). Further, the behavior of the ligands (bbma, bbms, bbes) at different pH conditions was determined on the basis of ¹³C NMR studies. The redox potentials [Co(II)/Co(I)] of the complexes follow the trend [Co(bbma)₂]²⁺ < [Co(bbms)₂]²⁺ ≈ [Co(bbes)₂]²⁺ which demonstrates the stabilization of the Co(II) ion is more by both weak σ-donor and weak π-acceptor ligands rather than by σ-donor ligand.     

Luminescence of Eu and Ce in K3Ca2(SO4)3F fluoride material

A new halophosphor K₃Ca₂(SO₄)₃ F activated by Eu or Ce and K₃Ca₂(SO₄)₃ F:Ce,Eu co‐doped halosulfate phosphor has been synthesized by the co‐precipitation method and characterized for its photoluminescence (PL). The PL emission spectra of the K₃Ca₂(SO₄)₃ F :Ce phosphor show emission at 334 nm when excited at 278 nm due to 5d → 4f transition of Ce³⁺ ions. In the K₃Ca₂(SO₄)₃ F:Eu lattice, Eu²⁺ (440 nm) as well as Eu³⁺ (596 nm and 615 nm) emissions have been observed showing ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ transition of the Eu³⁺ ion, which is in the blue and red region of the visible spectrum respectively. The trivalent europium ion is very useful for studying the nature of metal coordination in various systems owing to its non‐degenerate emitting ⁵D₀ state. K₃Ca₂(SO₄)₃ F:Ce,Eu is suitable for Ce³⁺ → Eu²⁺ → Eu³⁺ energy transfer in which Ce³⁺and Eu²⁺ play the role of sensitizers and Eu²⁺ and Eu³⁺ act as the activators. The observations presented in this paper are relevant for lamp phosphors. Copyright © 2015 John Wiley & Sons, Ltd.     

Supramolecular salts containing the anionic [Ge(C2O4)3] complex and heteroaromatic amines

The crystalline compounds (Hbipy)₂[Ge(C₂O₄)₃] (1) and (Hphen)₂[Ge(C₂O₄)₃] · 2(H₂O) (2) [Hbipy⁺ is the 2,2′-bipyridinium cation (C₁₀H₉N₂), and Hphen⁺ is the 1,10′-phenathrolinium cation (C₁₂H₉N₂)] were isolated from mild hydrothermal syntheses and their structures were elucidated from single-crystal X-ray diffraction. The two compounds were further characterised by vibrational spectroscopy (FT-IR and FT-Raman), thermogravimetric analysis (TGA) and CHN elemental composition. Compounds 1 and 2 comprise the tris(oxalato-O,O′)germanate dianion complex, [Ge(C₂O₄)₃]²⁻, which co-crystallises with Hbipy⁺ (in 1), or Hphen⁺ and water molecules (in 2). In 1, the germanium oxalate anionic complex, [Ge(C₂O₄)₃]²⁻, and the Hbipy⁺ organic residues interact mutually via N-H?O hydrogen bonding interactions, leading to supramolecular discrete hydrogen-bonded units which are further interconnected via π-π stacking. Compound 2, on the other hand, exhibits a more complex hydrogen bonding network due to the presence of the water molecules of crystallisation which, along with π-π stacking between neighbouring Hphen⁺ residues, mediate the crystal packing.     

A novel ferromagnetic coupling one-dimensional complex {Cu(II)(NIT3Py)2[N(CN)2]2(H2O)2}

The novel ferromagnetic coupling one-dimensional complex {Cu(NIT3Py)₂[N(CN)₂]₂(H₂O)₂} (NIT3Py=2-(3^′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group C2/c. The Cu(II) ion is in a distorted octahedral environment. The units of {Cu(NIT3Py)₂[N(CN)₂]₂(H₂O)₂} were connected as one-dimensional structure by the intermolecular hydrogen bonds. Magnetic measurements show that there are intramolecular ferromagnetic interactions and intermolecular antiferromagnetic interactions within the chain.     

Eu3+ (orange/red) luminescence in LiXSO4Cl (X = Mg,Zn) halosulfate phosphor

The wet chemical synthesis, X‐ray diffraction and photoluminescence characteristics in alkaline halosulfate phosphors such as LiMgSO₄Cl:Eu and LiZnSO₄Cl:Eu are reported in this paper. The effect of Li ion on Eu³⁺ luminescence (⁵D₀ → ⁷F₂ electronic transition) and incorporation of Eu³⁺ ion in lithium base alkaline halosulfate phosphor has been studied. Copyright © 2009 John Wiley & Sons, Ltd.     

Luminescence in Li3Al2(PO4)3:Eu2+

A series of efficient Li₃Al₂(PO₄)₃:Eu²⁺ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li₃Al₂(PO₄)₃ phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li₃Al₂(PO₄)₃:Eu²⁺ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu²⁺ was observed in Li₃Al₂(PO₄)₃:Eu²⁺ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu²⁺ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Optical properties of Eu2+/Eu3+ mixed valence phosphor Ca2SiO2F2:Eu2+/Eu3+

The Eu²⁺/Eu³⁺ mixed valence phosphor Ca₂SiO₂F₂:Eu²⁺/Eu³⁺ was prepared using a solid‐state reaction synthesis method in a CO atmosphere, and the optical properties were investigated. The spectroscopic properties revealed that Ca²⁺ ions were occupied by both Eu²⁺ and Eu³⁺ ions in Ca₂SiO₂F₂, and both ions were able to generate their characteristic emissions. A broad 5d → 4f Eu²⁺ band at ~470 nm and narrow 4f → 4f Eu³⁺ peaks upon excitation with n‐UV light were observed. The ratio between Eu²⁺ and Eu³⁺ emissions changed regularly, and the relative intensity of the red component from Eu³⁺ became systematically stronger with increasing overall Eu content. As a result, the emission color of these phosphors can be tunable from blue to pink under n‐UV light excitation.     

One-pot synthesis of the decaniobate salt [N(CH3)4]6[Nb10O28] · 6H2O from hydrous niobium oxide

A robust and easily reproducible one-pot synthetic method for the preparation of [N(CH₃)₄]₆[Nb₁₀O₂₈] · 6H₂O is introduced.     

Spectral investigations on Eu3+,Sm3+‐doped and Sm3+/Eu3+ co‐doped potassium‐fluoro‐phosphate glass emitting intense orange‐red for lighting applications

Potassium fluoro‐phosphate (KFP) glass singly doped with different concentrations of europium (Eu³⁺) or samarium (Sm³⁺) or co‐doped (Sm³⁺/Eu³⁺) was prepared, and their luminescence spectra were investigated. The phase composition of the product was verified by X‐ray diffraction analysis. Optical transition properties of Eu³⁺ in the studied potassium phosphate glass were evaluated in the framework of the Judd–Ofelt theory. The radiative transition rates (A_R), fluorescence branching ratios (β), stimulated emission cross‐sections (σ_e) and lifetimes (τ_exp) for certain transitions or levels were evaluated. Red emission of Eu³⁺ was exhibited mainly by the ⁵D₀→⁷F₂ transition located at 612 nm. Concentration quenching and energy transfer were observed from fluorescence spectra and decay curves, respectively. It was found that the lifetimes of the ⁵D₀ level increased with increase in concentration and then decreased. By co‐doping with Sm³⁺, energy transfer from Sm³⁺ to Eu³⁺ occurred and contributed to the enhancement in emission intensity. Intense orange‐red light emission was obtained upon sensitizing with Sm³⁺ in KFP glass. This approach shows significant promise for use in reddish‐orange lighting applications. The optimized properties of the Sm³⁺/Eu³⁺ co‐doped potassium phosphate glass might be promising for optical materials.     

Synthesis of AlN: Eu2+ green phosphors by a simple direct nitridation method

Eu‐doped aluminum nitride phosphors were successfully prepared using simple direct nitridation of a metallic aluminum and Eu₂O₃ powder mixture in flowing ammonia. AlN formed at reaction temperatures >900°C, and Eu³⁺ transformed into the secondary oxide phase EuAl₂O₄ in the nitridation condition. Phase pure AlN was obtained by post‐heat treatment of the nitridated product at 1600°C for 3 h in a nitrogen atmosphere, with an Eu²⁺ doping concentration < 0.5%. The phosphors exhibited broad green emission centered at 521 nm under 363 nm excitation. The luminescence of the phosphor was significantly influenced by the post‐heat treatment temperature, which affected the dissolution of Eu²⁺, phase purity, crystallinity, and particle size of the AlN host.     

Tunable luminescence properties and energy transfer in LaAl11O18:Eu,Tb phosphor

Eu²⁺ and Tb³⁺ singly doped and co‐doped LaAl₁₁O₁₈ phosphors were prepared by a combustion method using urea as a fuel. The phase structure and photoluminescence (PL) properties of the prepared phosphors were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra. When the content of Eu²⁺ was fixed at 0.01, the emission chromaticity coordinates could be adjusted from blue to green region by tuning the contents of Tb³⁺ ions from 0.01 to 0.03 through an energy transfer (ET) process. The fluorescence data collected from the samples with different contents of Tb³⁺ into LaAl₁₁O₁₈: Eu, show the enhanced green emission at 545 nm associated with ⁵D₄ –⁷F₅ transitions of Tb³⁺. The enhancement was attributed to ET from Eu²⁺ to Tb³⁺, and therefore Eu²⁺ ion acts as a sensitizer (an energy donor) while Tb³⁺ ion as an activator. The ET from Eu²⁺ to Tb³⁺ is performed through dipole–dipole interaction. The ET efficiency and critical distance were also calculated. The present Eu²⁺–Tb³⁺ co‐doped LaAl₁₁O₁₈ phosphor will have potential application for UV convertible white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.