The single crystal and crystallized powder of triphosphate CeP3O9 have been syn-thesized,and the space group of CeP3O9 has been determined to be C2221 with the cell parameters of a=8.6059,b=11.2437,c=7.3518 ,V=711.4(3) 3,Z=4,Dc=3.520 g/cm3,F(000)=700,R=0.0377 and wR=0.0930. The absorption and emission spectra have been measured,for which the strongest absorption and emission peaks are located at 280 and 320 nm,respectively. The density of state (DOS) and dielectric function have been calculated by the DFT method. The crystal is transparent provided the wavelength is larger than 341 nm,and the observed ultraviolet cut-off edge is at about 350 nm for a polycrystalline power sample. It is possible that the triphosphate CeP3O9 will become an ultraviolet emission material.
TONG Hua-Nan ZHANG Hao CHENG Wen-Dan WU Dong-Sheng GONG Ya-Jing ZHU Jing HUANG Shu-Ping ZHAO Dan
Alkali metal-rare earth polyphosphates, CsLn(PO3)4 (Ln = La, Ce), were synthe- sized by the high temperature solution reaction and studied by single-crystal X-ray diffraction technique. They crystallize in the monoclinic space group P21 (Z = 2) and feature infinite PO4 spiral chains linked with neighboring CsO10 and LnO8 polyhedra. In addition, theoretically calculated energy band structure and density of states (DOS) by the density functional theory (DFT) predict that the solid-state compound CsLa(PO3)4 possesses insulative character.
We present a first principle study of Cr-doped In2O3 system using density func-tional theory. The obtained results show that the Cr ion prefers the cation site of the center of trigonally distorted octahedron and converges to high spin-polarized configuration in the ground state. The hybridization between d-states and the donor states is strong, and the spin-split donor impurity-band model is found to be the most favorable mechanism for the ferromagnetism in this system. The good ferromagnetic property of high Curie temperature is discussed in view of the electronic structure analyses.
The silver-dppm complex, [Ag2(dppm)2(NMP)2](SbF6)2?4H2O?3CH2Cl2 1 (NMP = 2- (4-dimethylaminophenyl)imidazo(4,5-f)(1,10)phenanthroline, dppm = diphenylphosphinomethane), was synthesized and its structure was determined by X-ray diffraction. The crystal belongs to mono- clinic, space group C2/c, Mr = 2461.61, a = 21.57(10), b = 22.48(6), c = 22.53(6) ?, β = 101.29(2)o, V = 10713(64) ?3, Z = 4, Dc = 1.526 g/cm3, μ = 1.141 mm?1, F(000) = 4920, R = 0.0664 and wR = 0.1774 for 8524 observed reflections (I > 2σ(I)). Complex 1 exists as a centrosymmetric dimmer. The two dppm molecules bridge two AgNMP moieties to form an eight-membered Ag2P4C2 metal- lacyclic ring with ligand NMP chelating to each Ag. It appears photoluminescence (λmax = 625 nm) at room temperature and makes red shift compared with free ligand NMP (λmax = 522 nm). DFT calculation indicates that the emission of 1 originates from singlet metal-perturbed ILCT excited state.
A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate li- gands, [Bu4N][(CO)4Mo(μ-SC6H5)2Mo(C5H10dtc)(CO)2] 1 (C5H10dtc = S2CNC5H10), has been pre- pared by reaction of [Mo2(SC6H5)2(CO)8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162(3), b = 17.466(2), c = 20.453(4) ?, β = 100.77(1)°, Z = 4, V = 4619(2) ?3, C40H56Mo2N2O6S4, Mr = 980.95, Dc = 1.389 g/cm3, μ = 7.66 cm?1, F(000) = 1988 and R = 0.0746 for 5161 observed reflections with I > 2σ(I). The complex contains a [Mo2S2]2? planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.
