Solvothermal Synthesis, Structure and the Secondorder NLO Properties of a Novel Non-metal 3-D Borophosphate:（NH4）2[B2P2O8（OH）2]

A new non-metal 3-D borophosphate compound formulated as(NH4)2[B2P2O8(OH)2](1)has been synthesized by a solvothermal method and characterized by elemental analysis,energy-dispersive X-ray spectroscopy(EDS),IR spectrum and single-crystal X-ray diffraction.The borophosphate(NH4)2[B2P2O8(OH)2]crystallizes in the cubic system,space group P213 with Z=2,a=b=c=7.586(4)?,V=436.6(4)?3,Mr=281.64,Dc=2.127 g/cm^3,λ=0.71073?,μ=0.551 mm^-1,F(000)=284,R=0.0277 and wR=0.0758 for 262 observed reflections with I>2σ(I)and S=1.082.Its structure is constructed by the connection of PO4 and BO3(OH)tetrahedra to form a 3-D anionic framework containing 4-and 8-membered rings(MRs),with two NH4+cations located in the channels of the 8-membered rings.The N–H…O hydrogen bonds are observed in its packing structure and enhanced the stability of crystal structure.In addition,its thermal stability,UV spectrum and second-order NLO properties have been also investigated.

A Novel Borophosphate Coordination Polymer with Sandwich-type Supramolecular Architecture

A novel borophosphate (Hmel)3{Co2[(mel)2(HPO4)2(PO4)]·H3BO3·H2O} (mel= melamine) has been synthesized under mild solvothermal conditions. The structure of the compound exists a high ordered organic-inorganic sandwich-type supramolecular architecture via metal-coordination, hydrogen bonds and π-π stacking interactions.

Open-framework Borophosphate:(NH4)_(0.5)Fe^II_(0.5)Fe^III_(0.5)(H_2O)_2BP_2O_8·0.5H_2O

An open-framework ammonium ferricborophosphate compound was synthesized by mild hydrothermal condition at 110C. The crystal structure has been determined by single-crystal X-ray diffraction analysis: hexagonal, P6522, a = 9.452(2) , c = 15.698(5) , a = 90, g = 120, Z = 6, Mr = 310.58, V = 1214.0(5) 3, Dc = 2.549 g/cm3, m = 2.311mm-1, F(000) = 930. The chiral tetrahedral-tetrahedral helical ribbons are linked by the mixed valance FeII/FeIIIO6 coordinated octahedra. The ammonium ions are located inside the free loop of helical ribbons close to the inner wall of the helical channels1{[BP2O8]3-}, effecting on balancing charge and stabilizing helical ribbons.

Crystal Structure of Borophosphate with 6_1 Screw Axis Helices

A brilliant purple octahedral single crystal is hydrothermally synthesized by the reaction of CoCl26H2O, H3BO3 and H3PO4 in NaOH aqueous solution of CH3(CH2)15N(CH3)3Br, and its crystal structure has been characterized by single-crystal X-ray diffraction. The compound, NaCo(H2O)2BP2O8稨2O (Mr = 336.72), belongs to hexagonal, space group P6122 with a = 9.447(5), c = 15.83(1) , V = 1223(1) 3, Dc = 2.742 g/cm3, Z = 6, F(000) = 1002 and m = 2.606 mm-1. The three-dimensional framework in the compound is built up from the linkage tetrahedral ribbons, in which the BO4 and PO4 tetrahedra alternate with CoO6 octahedra. The sodium ions and water molecules are located within the free thread of the helical ribbons.

Synthesis and Crystal Structure of a Novel Borophosphate Compound with Noncentrosymmetric:Cd_3BPO_7

A new borophosphate compound Cd3 BPO7（Mr = 490.98） has been successfully synthesized by conventional high temperature solid state reaction for the first time and its structure was determined by single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group Pna21, with a = 13.247（3）, b = 8.8217（18）, c = 5.0792（10）, V = 593.56（20）3, Z = 4, Dc = 5.494 g/cm3, λ（CuKα） = 1.5406, F（000） = 880, the final R = 0.0212 and wR = 0.0513 for 1287 observed reflections（I 〉 2σ（I））. In the crystal structure of Cd3 BPO7, the Cd（II） forms a slightly distorted octahedral geometry, BO3 3- and PO4 3- ions linking adjacent Cd（II） ions to form a 3D network. The second harmonic generation（SHG） on powder samples was measured using Kurtz and Perry technique. The result indicates that Cd3 BPO7 exhibits a SHG response 2.2 times larger than that of potassium dihydrogen phosphate（KDP） and is phase-matchable.

KCdBP2O7(OH)2:a New Cadmium Borophosphate with a 2D Layer Framework

A new cadmium borophosphate, KCdBP2O7（OH）2, was synthesized by using boric acid flux method. The crystal structure was determined by single-crystal X-ray diffraction analysis （monoclinic, space group P21/c, a = 12.103（2）, b = 8.8737（18）, c = 7.1266（14）A^°, β = 101.69（3）°, V = 749.5（3） A^°3 and Z = 4）. The framework of KCdBP2O7（OH）2 is constructed from the connection of infinite [CdO6] octahedral chains and open-branched chains [（BP2Φ9）2]n （Φ = O, OH）, giving rise to a 2D layered structure viewed along the [100] direction. The K＋ ionic conductivity measured for KCdBP2O7（OH）2 was 3.47 × 10^-8 S·cm^-1 at 583 K.

A novel Eu^(3+)-doped phosphor-in-glass for WLEDs and the effect of borophosphate matrix

Phosphor-in-glass(PiG)is a potential color convertor for high power WLEDs.A novel glass matrix with advanced performance is still a challenge.Recently,Eu^(3+)doped glass matrix has attracted much consideration mainly due to its red compensation.A new borophosphate matrix to realize Eu^(3+)red light was designed in the Na_(2)O-ZnO-P_(2)O_(5)-B_(2)O_(3)-Eu_(2)O_(3)system.Meanwhile,a series of PiGs composed of different concentrations of Y3Al5O12:Ce phosphor and the matrix were also fabricated by re-sintering.The crystallization of Eu^(3+)based phosphate offers a novel red emission quenching apart from normal concentration quenching in the glass system.No direct energy transfer but only little reabso rption occurs between Eu^(3+)and Ce^(3+)ions.The Ce^(3+)concentration effect is obvious on the electroluminescent color.The optimized color rendering index of 79.7,the CIE coordinates near natural white and the range of CCT from 3943 to 6097 K were obtained for the packaged white light emitting diodes(WLEDs)together with the excellent CCT stability higher than about 97.5%and the quadruple thermal conductivity than that of silicon resin.The work implies borophosphate glass based PiGs with fine transparence and energy conversion efficiency are promising for excellent WLEDs,while the LED by using the PiG sample without any yellow phosphor doped is of high color purity and has a potential use as the 465 nm blue source.

From borophosphate to fluoroborophosphate:a rational design of fluorine-induced birefringence enhancement

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_(2)BP_(3)O_(11)with the monoclinic space group P2_(1/c) has been synthesized in the sealed system.Ba_(2)BP_(3)O_(11)exhibits a rare P-O-P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_(4)]^(3-)with[BO_(3)F]^(4-),the first alkaline-earth metal/lead fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)with the same space group were designed.Since the scissors effect of fluorine,in M_(2)BP_(2)O_(8)F(M=Ba and Pb),a BO_(3)F tetrahedron corner-sharing with three PO_(4)tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_(n)(M=Ba/Pb,n=5,6,8)distorted polyhedra.The first principles calculation shows that the borophosphate Ba_(2)BP_(3)O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.

Structural and luminescence studies of europium ions in lithium aluminium borophosphate glasses

Eu3＋ doped borophosphate glasses with the chemical composition 20Li2O-30Al2O3-10B2O3-40P2O5-xEu2O3（where x=0.05 mol.%, 0.1 mol.%, 1.0 mol.%, 1.5 mol.% and 2.0 mol.%） were prepared by conventional melt quenching technique. The structural and luminescence properties of the prepared Eu3＋ doped borophosphate glasses were studied and compared with reported results. The XRD pattern showed the amorphous nature of the prepared glasses. Whereas, the FTIR spectra revealed the vibrational modes in the prepared glasses. The bonding parameters（ β and ？） were calculated through the excitation spectra. Judd-Ofelt（J-O） intensity parameters were calculated from the emission spectra and were used to determine transition probability（A）, stimulated emission cross-section（σE P）, radiative lifetime（τR） and branching ratios（βexp） for the transition 5D0→7Fj（j=1, 2, 3 and 4） of Eu3＋ ions. Furthermore, the luminescence intensity ratio（R） of 5D0→7F2 to 5D0→7F1 transition was also calculated. Transition 5D0→7F2 had the highest value of stimulated emission cross-section and branching ratios and the results were comparable with the reported values. This indicated that the present glass is promising host material for Eu3＋ doped fiber amplifiers.

Color tuning of Eu-Tb co-doped borophosphate glasses for white light through valence state adjustment

The dependence of color points of white light on the composition of bomphosphate glasses co-doped with europium （En） and terbium （Tb） has been investigated in terms of valence change of rare earth ions. Under ultraviolet （UV） excitation, the white light is observed to be from a combination of 4f65d → 4f7 band transition emission at 425 nm for Eu^2＋, 5D0 → ^7Fj （J= 1, 2） lineemissions at 593 nm and 611 nm for Eu^3＋, and 5D4 → 7F5 band transition emission at 545 nm for Tb^3＋. By varying the glass composition, the resultant emission color can be tuned efficiently. Eventually, the optimized white light with commission international de I＇Eclairage （CIE） coordinate of （0.3382. 0.2763） and the correlate color temperature （CCT） at 5010 K are achieved.

Synthesis, Structure, Thermal and Magnetic Properties of a New Open-framework Borophosphate： NH4Mn（H2O）2BP2O8·H2O

Using new template agent, a new borophosphate compound, NH4Mn（H2O）2BP2O8·H2O was hydrothermally prepared and structurally characterized. It crystallizes in a hexagonal space group P6 1 22 with lattice parameters a= 0.9652（2） nm, c= 1.5792（5） nm, V= 1.2740（5） nm^3 and Z=6. The structure has a three-dimensional open-frame work with borophosphate helical ribbons ^1∞{ [BP2O8 ]^3-} and MnO4（H2O）2 octahedra. The water molecules are positioned inside the helical channels. Very interestingly, the ammonium ions are located outside the loop of the free helical ribbons via the strong hydrogen bonds, which is different from the borophosphate analogue reported. The magnetization of the title compound is paramagnetic down to 5 K of the Curie-Weiss type within the measured range of 5=-00 K with θ=-7.3 K, indicative of very weak antiferromagnetic interactions. The thermal decomposition of the compound was also described.

Studies of Anomalies in Mixed Conduction of Na2O and V2O5 Doped Boro-Phosphate Glasses

A set of borophosphate glasses doped with alkali and transition metal (TM) ions have been synthesized. The glasses were carried through;annealing, XRD, density, DC conductivity studies. Molar volume and density varied nonlinearly. High temperature activation energy is analysed taking into consideration of Mott’s SPH model. The low temperature electrical conductivity was analysed by Mott and Greaves VRH. Several polaron hopping related parameters at high temperature region and density of states at low temperature region were computed. The high temperature DC activation energy measured by conductivity, calculated numerous pertained parameters varied nonlinearly with mole fraction of vanadium content. The Study exhibits DC electrical conduction is due to both alkali and transition metal ions and thus confirms the mixed conductivity. A crossover conduction mechanism from the ionic dominant region to polaronic predominant region has been also observed. Studies revealed the single transition effect at 0.4 mol fraction of V2O5 content.