硼酸钾锶晶体的高温溶液法生长研究

以摩尔比为3∶1的NaF和H3 BO3为复合助熔剂,采用高温溶液法生长出了尺寸达7×4 ×3 mm3的较透明的KSr4B3O9单晶,并探讨了生长KSr4B3O9晶体助熔剂体系的选择.该晶体属正交晶系,空间群为Ama2,晶胞参数为:a=109.87(2) nm,b =119.48(2) nm,c =68.865(2) nm.该晶体结构是由KO10基团,SrOx(x=8,9)基团和独立的BO3三角形相互连接构成的三维网络结构;UV-Vis-NIR漫反射光谱说明KSr4B3O9化合物在紫外区230 nm左右才表现为全吸收;粉末倍频测试结果表明该化合物总的倍频效应与KH2PO4 (KDP)相当.     

具有倍频效应的硼酸盐Pb2 [B5O9]Br化合物的合成、晶体生长及其性质研究

利用高温固相反应法合成出Pb2 [B5O9]Br硼酸盐粉末.采用PbO-NaF做复合助熔剂,利用顶部籽晶法获得了3 mm ×3 mm ×1.5 mm的透明单晶,X射线粉末衍射数据显示,该晶体属正交晶系,Pnn2空间群,晶胞参数为a=1.1524(1) nm, b=1.1431(1) nm, c=0.65399(3) nm. 红外光谱测量证实晶体结构中含有BO3-3和BO5-4基团.反射光谱表明Pb2 [B5O9]Br的紫外吸收边在250 nm左右.Pb2 [B5O9]Br粉末倍频效应(SHG)测试表明该化合物具有非线性光学效应,信号强度约等同于β-BaB2O4.     

Na3La2(BO3)3的晶体结构

以Na2CO3-H3BO3-NaF为助熔剂,使用顶部籽晶法生长出Na3La2(BO3)3透明单晶.测定了Na3La2(BO3)3的晶体结构,该晶体属正交晶系,空间群:mm2(No.38),晶胞参数为a＝0.51580(10)nm,b=1.1350(2)nm,c=0.73230(15)nm,α＝β＝γ＝90°,V＝0.42871(15)nm3,密度:.053g/cm3.晶体结构中的硼氧基团是平面的BO3基团,BO3基团相互独立,且与Na(1)O6、Na(2)O8、Na(3)O6和La(1)O9配位多面体连结形成三维网络骨架结构.讨论了Na3La2(BO3)3的晶体结构与倍频效应的关系.     

掺杂BaAlBO3F2晶体的生长及性能研究

本文通过对BaAlBO3F2(BABF)晶体进行掺杂以增加晶体的双折射率,从而使BABF晶体的最短直接倍频波长紫移,拓宽其应用波段.研究发现Ga掺杂能够使BABF晶体的最短直接倍频波长从273 nm紫移至259.5 nm理论上能够实现四倍频(266 nm)激光输出.采用优化的B2O3-LiF-NaF助熔剂体系,通过中部籽晶法生长出尺寸为25 mm×20 mm×10 mm的Ba(Al,Ga) BO3F2晶体.对该晶体的透过光谱、光学均匀性、弱吸收、倍频匹配曲线、粉末倍频效应和激光损伤阈值的性能进行了表征,结果显示了该晶体在紫外波段激光输出的潜能.     

K3B6O10Br非线性光学晶体的生长及性质研究

采用顶部籽晶法,KF.2H2O-PbO复合助熔剂生长K3B6O10Br晶体,获得了18 mm×18 mm×10 mm尺寸的单晶。K3B6O10Br紫外透过截止边约为210 nm,粉末倍频效应为3倍KDP,利用德拜公式计算了阴离子基团的偶极矩。采用直角棱镜法测试了晶体折射率并拟合了Sellmeier方程。计算及实验表明,K3B6O10Br能够实现532 nm及355 nm倍频输出。对晶体的激光损伤阈值、硬度及潮解性进行了测试。     

非线性光学晶体Ba2B5O9Cl的合成、晶体生长及性能的研究

首次以LiF-H3BO3为助熔剂,用顶部籽晶法,生长出尺寸为12 mm×13mm×5mm的Ba2B5O9Cl透明单晶.通过热性能分析证实该晶体为非同成分熔融化合物,属于正交晶系,空间群Pnn2,晶胞参数为a=1.1576(2) nm,b=1.1619(2)nm,c =0.66874(13) nm,V=0.8994(3) nm3,Z=4.该晶体中含有BO3和BO3基团,具有三维网状的晶体结构.Ba2B5O9Cl粉末的非线性光学效应约为KDP的3.5倍,同时还进行了红外、漫反射光谱性能的研究.     

硼酸锶钡(Ba0.87Sr3.13B14O25)晶体的生长、结构和性质研究

本文报道了一种新的硼酸盐化合物-Ba0.87Sr3.13B14O25,采用泡生法已生长出尺寸为35mm×25mm×5mm的晶体.该晶体为单斜晶系,C2/m空间群,a=1.6425(3)nr,b=0.77739(16)nm,c=1.6665(3)nm,β=119.22(3)°,Z=4.结构中B3O8六元环通过O原子和BO3三角形相互连接,构成三维的硼氧阴离子骨架,金属阳离子占据多面体间的空隙.测量了BSBO晶体的透过谱,该晶体的显微硬度为578kg/mm2.     

具有非对称中心结构的硼酸盐Bi2ZnB2O7的合成、晶体结构和光学性质

具有非对称中心结构的硼酸盐Bi2ZnB2O7由固相反应法在低于700℃下制备得到.X射线单晶结构分析表明,该化合物以正交空间群Pba2结晶,晶体学参数为:a=1.0819(2)nm,b=1.1023(2)nm,c=0.4890(1)nm,Z=4.其晶体结构中包含分别由[BO3]3-和[BO4]5-组成的[B2O5]4-和[B2O7]8-基团,它们被[ZnO4]四面体通过共用O原子的方式连接成二维2∞[ZnB2O7]6-层,这些层由Bi3+离子进一步结合形成三维网.红外光谱证实了[BO3]3-和[BO4]5-基团的存在,粉末倍频效应测试表明,其强度为KDP(KH2PO4)的4倍,UV漫反射光谱表明该物质吸收边约为360 nm.     

非线性光学晶体Na3La9O3(BO3)8的生长研究

以Na3CO3和H3BO3为助熔剂,Na3CO3和H3BO3摩尔比为7/6,熔质Na3La9O3(BO3)8和助熔剂摩尔比为1/10～1/14,采用顶部籽晶生长方法,生长Na3La9O3(BO3)8晶体,晶体尺寸为30×18×8mm3.本文讨论了籽晶方向对Na3La9O3(BO3)8晶体生长的影响,(100)方向比(001)方向更有利于晶体生长.     

掺铒硼酸钙氧钆(GdCOB:Er)晶体的光谱分析

生长并测量了新型激光晶体GdCa4O(BO3)3:Er(简称GdCOB:Er)的透过谱,计算了Er3+离子在晶体中的吸收截面.由积分吸收截面的公式拟合出唯象强度参量Ω2＝2.531×10-20cm2,Ω4＝2.716×10-20cm2,Ω6＝1.891×10-20cm2,并应用Judd-Ofelt理论计算出振子强度fJ,J、辐射跃迁几率AJ,J、荧光辐射寿命τ及积分发射截面σ.并根据这些光学参量,讨论了GdCa4O(BO3)3:Er晶体用作激光晶体的可能性.     

Crystal and molecular structures oftrans-dichloro-(ethylene) (4-methylpyridine)platinum(II) andtrans-dichloro(ethylene) (2,4,6-trimethylpyridine)platinum(II)

The crystal and molecular structures oftrans-[PtCl₂(C₂H₄)(4-MeC₅H₄N)] (I) andtrans-[PtCl₂(C₂H₄)(2,4,6-Me₃C₅H₂N)] (II) have been determined by single-crystal x-ray methods.I crystallizes in space groupP2₁/c witha= 4.991(1), b=21.658(3), c=10.675(3) Å, =110.17(2) °,Z=4;II is orthorhombic (Pbca) witha=10.295(6),b=12.393(8),c=20.370(10) Å,Z=8.Full-matrix least-squares refinements have given finalR factors of 0.053 (1520 reflections) forI and 0.042. (1412 reflections) forII. The intensities were recorded by counter methods, and only those reflections havingI>3(I) were used in the analyses.In both complexes, platinum is four-coordinate with the two chlorine atoms, the double bond of the ethylene, and the nitrogen atom of the substituted pyridine. The two structures are discussed in terms of the arrangement of the pyridine ligand with respect to the PtCl₂(C₂H₄) moiety.     

Synthesis, spectroscopy, and X-ray structures of fac-(CO)3(dppe)MnSC(S)H, fac-(CO)3(dppe)ReSC(S)H, fac-(CO)3(dppp)ReSC(S)H, and fac-(CO)3(dppb)ReSC(S)H

The monodentate dithioformato complexes, fac-(CO)₃(dppe)MnSC(S)H (1), fac- (CO)₃(dppe)ReSC(S)H (2), fac-(CO)₃(dppp)ReSC(S)H (3), and fac-(CO)₃ (dppb)ReSC(S)H (4), where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane, were synthesized from the treatment of the corresponding hydrides, fac-(CO)₃ (P-P)MSC(S)H with CS₂. Compounds 1–4 crystallize in the monoclinic crystal system: for 1, space group = P2₁/c, a = 15.3139(3) Å, b = 9.7297(4) Å, c = 19.0991(6) Å, = 105.928(1), V = 2736.5 ų, Z = 4; for 2, space group = P2₁/c, a = 15.6395(8) Å, b = 9.8182(5) Å, c = 19.4153(11) Å, = 106.741(1), V = 2854.9(3) ų, Z = 4; for 3, space group = P2₁/n, a = 11.3570(10) Å, b = 19.465(2) Å, c = 15.5702(14) Å, = 104.776(2), V = 3328.3(5) ų, Z = 4; and for 4, space group = C2/c, a = 32.078(2) Å, b = 10.4741(6) Å, c = 19.0608(9) Å, = 94.315(2), V = 6386.1(6) ų, Z = 8.     

Structure of (chloranilato)bis(tri-n-butylphosphine)palladium(II)

(Chloranilato)bis(tri-n-butylphosphine)palladium(II), [Pd(C₆Cl₂O₄){P(C₄H₉)₃}₂] (chloranilic acid=2,5-dichloro-3,6-dihydroxy-p-benzoquinone): FW=718.02,P2₁/c,a=21.729(6),b=17.293(5),c=21.010(9) Å,=112.62(3)°,V=7287.42 ų,Z=8,D _c=1.309mg m^–3, Mo, =0.710730 Å,=0.76 mm^–1,F(000)=3008, finalR=0.087, 2594 observed reflections. Palladium is ligated by a distorted square planar P₂O₂ coordination sphere in the title compound. The two molecules per asymmetric unit differ in the arrangement of phosphine n-butyl chains, yielding two unique metal centers.     

Crystal structure of triphenylphosphine-(1-(di(trifluoromethyl)-hydroxymethyl)-cyclopentadienyl)-(1,2-di(carboxymethyl) ethylene-1-yl) ruthenium (0)

The structure of triphenylphosphine — (1 — (di(trifluoromethyl) — hydroxymethyl) — cyclopentadienyl) — (1,2 — di(carboxymethyl)ethylene — 1 — yl) — ruthenium (0) has been studied by single-crystal X-ray diffraction techniques. This compound, [C₅ H₄(CF₃)2 COH] Ru(PPh₃)C2(CO₂Me)₂H, crystallizes in the triclinic space groupP¯1 witha =10.131,b= 15.107,c= 10.798 Å, = 102.14, = 107.04, = 89.64° andZ = 2. The structure was refined by block-diagonal least-squares methods to a finalR value of 0.042, including hydrogen atoms. The compound contains a dicarboxymethylethylene ligand coordinated to ruthenium both through a ketonic oxygen and through a metal--carbon -bond. An intramolecular hydrogen bond is observed. Details of the structure are reported, and the structures of several Ru(0) complexes are compared.     

X-ray crystal structures ofcis-bis(diphenylphosphinamide)tetracarbonylmolybdenum(0) andtrans-bis(N-methyl diphenylphosphinamide)tetracarbonylmolybdenum(0)

The X-ray crystal structures ofcis-Mo(CO)₄(Ph₂PNH₂)₂,I, andtrans-Mo(CO)₄(Ph₂PNHMe)₂,II, are presented. ComplexI crystallizes in the monoclinic space groupP2₁/c(a=13.433(1),b=12.2719(8),c=17.318(2)Å;=109.79(1)°;V=2686.1(8)ų;Z=4). ComplexII crystallizes in the triclinic space groupP¯1 (a=6.9986(8),b=10.328(1),c=11.241(2)Å,=107.58(1)°,=91.76(1)°, =101.28(1)°,V=756.1(4)ų,Z=1). The molybdenum coordination geometry in each complex is a slightly distorted octahedron. The molybdenum-carbon bond lengths for the carbonyls trans to phosphorus in complexI are shorter than those the carbonyls trans to other carbonyls. The average molybdenum-phosphorus distance inI (2.525(5)Å) is similar to those in other diphenylphosphinamide complexes and longer than the molybdenum-phosphorus distance inII in 2.4585(7)Å). The distance between two nitrogen atoms incis Mo(CO)₄(Ph₂PNH₂)₂ (3.74(3)Å) is significantly larger than the sum of their van der Waals radii (3.10 Å) indicating that the two nitrogens are not hydrogen bonded.     

Structure of (N-(2-hydroxyphenyl)-salicylaldiminopiperidino) Ni(II) complex

The crystal and molecular structure of the title complex, C₁₈H₁₉N₂O₂Ni, has been determined by direct methods. The compound crystallizes in the monoclinic crystal system witha=22.973(1),b=5.212(1),c=27.076(1)Å, β=106.46(1)°, space groupC2/c,V=3109.1(6)ų, Z=8, andD _x=1.51g cm^?3. The nickel atom is in a slightly distorted square-planar environment of two oxygens [Ni(1)?O(1) 1.824(3) and Ni(1)?O(2) 1.856(3)Å] and two nitrogens [Ni(1)?N(1) 1.849(3) and Ni(1)?N(2) 1.932(3)Å] with O?Ni?N angles between 85.7(1) and 97.1(1)°. The nickel atom is 0.006 Å out of the plane of its ligands.     

Crystal and molecular structures of trans-bis(acetonitrile)bis(bipyridine)ruthenium(II) perchlorate and trans-diamminebis(bipyridine)ruthenium(II) perchlorate

The structures of trans-[(MeCN)₂(bpy)₂Ru](ClO₄)₂(I) andtrans-[(NH₃)₂(bpy)₂Ru](ClO₄)₂(II) have been determined by single crystal X-ray diffraction methods. (I) forms monoclinic crystals in the space groupP2₁/c witha=8.399(2),b=10.406(2),c=15.590(3) Å,=93.78(2)° andZ=2 atT=293 K. The final refinement gaveR=0.040 for 2448 reflections withF _o ² >3(F _o ² ). (II) crystallizes in the triclinic space groupP¯1 witha=1.702(1),b=8.439(2),c=10.525(2) Å,=107.56(2),=104.63(1), =100.89(2)° andZ=1 atT=293 K. Refinement using 1878 reflections withF _o ² >3(F _o ² ) produced a finalR value of 0.036. Both of these structures have the ruthenium atom located on a crystallographic inversion center. The bipyridine ligands in both structures are in the bowed conformation as a means of circumventing the steric problems associated with the trans arrangement of the bipyridine ligands. The Ru-N(monodentate) distance is longer for the ammonia complex (2.106(3) Å) than for the acetonitrile complex (2.008(4) Å); there are no significant differences in the distances and angles of the two Ru(bpy)₂ frameworks.     

X-ray crystal structure of trans-bis(monoethanolamine) bis(saccharinato)nickel(II)

The crystal structure of trans-bis(monoethanolamine)bis(saccharinato)nickel(II), [Ni(C₇H₄NO₃S)₂(C₂H₇NO)₂], has been determined from X-ray diffraction data. The metal complex is monoclinic, with a = 11.0555(5), b = 8.9103(4), c = 11.3890(5) Å, = 105.0230(10)°, Z = 2, and space group P2_1/c . The structure consists of individual molecules. Two monoethanolamine molecules and two saccharinate anions coordinate the nickel atom forming a distorted octahedron. The monoethanolamine molecules act as a bidentate ligand and form five-membered trans chelate rings, which constitute the plane of the coordination octahedron, while two saccharinate ions behave as a monodentate ligand occupying the axial positions. Intermolecular hydrogen bonds link the molecules to form a three-dimensional infinite structure.