Synthesis, Crystal Structure and Calculated β Value of a Tetrahedral Zinc (II) Complex——Zn(2-NH_2py)_2Br_2

A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm－1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210－30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.

Hydrothermal Synthesis and Crystal Structure of Inorganic-organic Hybrid Compound [H_3NC_2H_4NH_2]VOPO_4

An inorganic-organic hybrid compound, [H_3NC_2H_4NH_2]VOPO_4 was synthesized by means of the hydrothermal method. It was crystallized in a monoclinic system, a space group P2_1/c, with the crystal cell parameters: a=0.92285(11) nm, b=0.72994(9) nm, c=0.98495(11) nm, β=101.280(3)°, V=0.65067(13) nm^3, M_r=223.02 g/mol, D_c=2.277 g/cm^3, Z=4, R=0.0315, ωR=0.0865, GOF=1.085. The VO_5N octahedra chains are corner-linked by PO_4 tetrahedra; the VO_5N octahedra are all trans-linked with V—O bonds being alternately short and long. The monoprotonated ethylenediamine was intercalated between the layers with one end coordinating to V and the other end as an H-bond donor interacting with a terminal O atom of PO_4 from a neighboring sheet. The elementary analysis, infrared spectrum characters and thermal stability were also given.

Synthesis, Crystal Structure and Characterization of Energetic Monovalent Copper Azide Complex: [Cu_2(dmpz)(N_3)_2]_n

A novel cuprous azide complex with the formula of [Cu2（dmpz）（N3）2]n（1, dmpz： 2,6-dimethylpyrazine） has been synthesized through hydrothermal synthesis with the reducibility of H3PO3 and structurally characterized by single-crystal X-ray diffraction method. Single-crystal X-ray diffraction analysis reveals the title complex represents a three-dimensional network structure featuring 2D [Cu N3]n plane units bridged by bridging dmpz ligands to form a 3D network. Research results reveal that 1 has lower impact sensitivity and friction sensitivity, which may be expected to become insensitive energetic material and have potential applications. Crystal data： monoclinic, space group C2/c, a = 17.8599（15）, b = 8.2889（5）, c = 14.8076（14） A, β = 113.2580（10）o, V = 2014.0（3） A3, Z = 8, S = 1.025, the final R = 0.0303, w R = 0.0825 for 1460 observed reflections with I 2σ（I） and R = 0.0386, wR = 0.0870 for all reflections. In addition, elemental analysis, IR, and sensitivity characterization are presented.

Solvothermal Synthesis and Crystal Structure of a Novel Inorganic-Organic Hybrid Material, Fe_2O(OH)(C_5H_4NCOO)SO_4

A novel inorganic organic hybrid material, Fe 2O(OH)(C 5H 4 ~NCOO)SO 4 was synthesized via solvothermal route using a reaction of FeCl 3·6H 2O, KCNS, and 4 cyanopyridine in aqueous solution of H 2O 2 and ethanol at 130 ℃ for 3 d. The compound crystallized in monoclinic space group P 2 1, with cell parameters a =0 73850(15) nm, b =0 65100(13) nm, c =1 0546(2) nm, β =90 36(3)°, V =0 50700(18) nm 3 and Z =2. The structure is constructed with inorganic layered [Fe 2O(OH)SO 4] + cations linked by organic (C 5H 4NCOO) - anions. The compound is thermally stable up to approximately 240 ℃.

Hydrothermal Synthesis, Crystal Structure and Optical Properties of [M（en）3]（ndt）·H2O （M=Ni^Ⅱ, Co^Ⅱ, Mn^Ⅱ and ndt= 1,5-Naphthalenedithiolate）

Three novel compounds [Ni（en）3]（ndt）·H2O （1）, [Co（en）3]（ndt）·H2O （2） and [Mn（en）3]（ndt）·H2O （3） （en= ethylenediamine, ndt= 1,5-naphthalenedithiolate） have been synthesized under hydrothermal conditions, The structures were characterized by single crystal X-ray diffraction and all belong to monoclinic space group Cc. The [M（en）3]^2＋ cations （M=Ni^Ⅱ, Co^Ⅱ, Mn^Ⅱ）, ndt anions and crystallized water molecules assemble an iso-structural three-dimensional network through H-bonding interactions. Optical absorption properties and band gaps of such three compouds were determined with UV/Vis/NIR diffuse reflectance spectra.

Synthesis and Structure of 4，5－bis（2，4－Dinitrophenylthio）－1，3－Dithiole－2－Thione

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Hydrothermal synthesis and characterization of two novel inorganic-organic hybrid materials

By using different organic ligands, two 3D inorganic-organic hybrid compounds Co(C4H4N2)(VO3)2 1 and Co(C12H12N2)(VO3)2 2 were synthesized by hydrothermal reaction and characterized by X-ray crystallography. Crystal data: 1. crystal system orthorhombic, space group Pnna, a=10.188(2), b=11.497(2), c=7.3975(15), V=866.5(3)3, Z=4, Dcalcd= 2.705 g/cm3; 2. crystal system triclinic, space group P1– (No. 2), a=8.3190(17), b=8.4764(17), c=11.183(2), α=95.48(3)°, β=92.03(3)°, γ=107.24(3)°, V=748.0(3)3, Z=2, Dcalcd=1.958 g/cm3. The framework of compound 1 contains both {Co(C4H4N2)} and infinite metavanadate chains. Crystal structure of compound 2 is constructed with inorganic {CoV2O6} layers across-linked by organic 1,2-bis(4-pyridyl) ethane ligands. The two compounds are thermally stable to approximately 410 °C and 350 °C, respec- tively. Their optical band gaps are determined to be 2.13 eV and 2.12 eV by UV-VIS-NIR diffuse reflectance spectra, which revealed their nature of semiconductor and optical absorption features.

Accurate design and synthesis of nonlinear optical crystals employing KBe_(2)BO_(3)F_(2) as structural template

In spite of decades of great efforts,it is still very challenging to realize accurate design and synthesis of second-order nonlinear optical(NLO)crystals.KBe_(2)BO_(3)F_(2)(KBBF)is the sole NLO material that can output deep-ultraviolet light by direct second-harmonic generation process,so it is an ideal choice to use KBBF as the structural template to design environment-friendly candidates with better growth habit based on the reported compounds.In this review,we will elaborate the accurate design and synthesis of high-performance NLO ma-terials from the perspective of microscopic crystal structure based on KBBF,hoping to provide deep understanding on how to rationally design and synthesize targeted compounds efficiently and quickly.In addition,according to multiple requirements on ultraviolet NLO crystals,including second-harmonic generation,cut-off edge,and birefringence,we propose a new concept so-called quality factor to comprehensively evaluate the overall per-formance of new ultraviolet NLO materials.This concept would help to directly and readily evaluate the ability of an ultraviolet NLO material to achieve practical NLO output.

Rational synthesis, structural characterization and the third-order nonlinear optical properties of two new M-Cu-S (M = Mo or W) clusters

By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2 Cu2 S4 (TDT)2-(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (PPh3 )2 · 0. 5CH3 CH2 OH·0. 5H2O (2) have been prepared and characterized by IR, UV-Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X-ray structure analysis. Both compounds crystallize in space group P 21/ n with lattice parameters a = 1.0956(3), b = 2. 2072(3), c =2.4340(3) nm, β=100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9), b = 2.2135(3), c = 2.4317(4) nm, β = 99. 63(8)°, V = 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane-like cluster core [M2Cu2S4] (M= Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third-order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four-wave mixing (DFWM) for the first time and these clusters exhibited relatively large nonlinear optical coefficients.

Optical Properties and Structural Perfection of Chicago Sky Blue 6B-doped KDP Crystals

KDP crystals doped with Chicago Sky Blue 6B（CSB-6B） were grown by traditional lowering temperature method.The optical properties and structural perfection of KDP crystals were investigated by transmittance spectra and high-resolution X-ray diffraction,respectively.The results indicate that CSB-6B tends to be incorporated into the pyramidal sector of KDP crystals（PyS-KDP） and lead to inclusions parallel to（101） face.Additionally,the transmittance of as-grown KDP crystals decreases as the amount of CSB-6B increases. Moreover,the rocking curves of PyS-KDP suggest that CSB-6B can deteriorate the structural perfection of PyS-KDP.

Crystal Structure and Properties of a Sodium Terbium Borate Na_(2.67)Tb_(2.11)B_3O_9

A new nonlinear optical crystal of sodium terbium borate （Na2.67Tb2.11B3O9, Mr = 573.14） was synthesized by solid reaction method. The colorless transparent single crystals were grown from the high temperature solution by employing NaBO2 as flux. The structure was deter- mined by single-crystal X-ray diffraction method. The compound crystallizes in the orthorhombic system, space group Amm2 with a = 5.0744（10）, b = 10.990（2）, c = 6.9078（14） A, V = 385.24（13） A3, Dc = 4.941 g/cm3, F（000） = 250, Z = 2, μ= 9.205 mm-1, the final R = 0.0253 and wR = 0.0610. Its three-dimensional network structure is constructed from isolated BO33-, Na（1）O8, Na（2）O6, Na（3）O6 and Tb（1）O9 polyhedra. Variable-temperature magnetic susceptibility measurements show the compound is paramagnetic （μj = 7.04 μb）. The intensity of the second harmonic generation of Na2.67Tb2.11B3O9 is 2.5 times that of KDP.

Optical Properties of Ce-Doped Lithium Niobate Crystals with Various Li/Nb Ratio

Ce-doped lithium niobate （LiNbO3） single crystals were grown from the melts with various Li/Nb molar ratios （0.750, 0.850, 0.946, 1.100, 1.250 and 1.380） by Czochralski method, while doping concentration of Ce was 0.1 mol%. Infrared spectra （IR） and Ultraviolet-visible absorption spectra （UV） of the crystals were measured to investigate the location of Ce ions and defect structure in crystals. The writing time, erasing time, photorefractive sensitivity and dynamic range were measured by two-wave coupling equipment. The results showed that Ce takes the place of Li lattice site, and the LiNbO3 crystal grown from the melt with Li/Nb ratio of 1.250 is stoichiometric crystal, which has the best properties due to the synergistic effect of Ce ion and Li/Nb ratio. Also the influence of various Li/Nb ratios on the defect structure and optical properties of the crystal was reported.

Crystal Structure of Ethanolamine 5-Nitrosalicylic Acid Organic Adduct

The title adduct (C18H24N4O12, Mr = 488.41) crystallizes in monoclinic, space group P21/c with a = 4.0514(19), b = 25.193(11), c = 10.751(5) ?, β = 95.070(8)o, V = 1093.0(9) ?3, Z = 4, Dc = 1.484 g/cm3, F(000) = 512, μ(MoKα) = 1.26 cm-1, T = 293 K, the final R = 0.0593 and wR = 0.0862 for 956 observed reflections with I > 2σ(I). The compound is a 1:1 adduct of ethanolamine and 5-nitrosalicylic acid. The nitrogen atom of ethanolamine is protonated. In this crystal there exist a number of hydrogen bonds which link the ethanolamine and 5-nitrosalicylic acid molecules to form a three-dimensional infinite network structure.

A Neutron Diffraction Study for the Crystal Structure of the Deuterium（hydrogen） L－Arginine Phosphate Monohydrate

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Crystal Structure of L-arginine Fluoroborate

The title compound C_6H(15)N_4O_2·BF_4, Mr=262.03,crystallized in orthorhombic belonging to space group P2_12_12_1,a=5.050(2),b=13.619(6),c=16.470(3)A.V=1133(1)A;Z=4 ;Dc=1. 536 gcm-3,F(000)=544,μ=1.462 cm￣(-1)(MoKα).The final R=0.082 and Rw=0. 081 for 673 independent observed reflections with I≥3σ(Ⅰ).The title compound is a 1:1 ionic complex of L-arginine and fluoroborate,and both the amino and guanidyl groups of L-arginine are protonated. There are a lot of hydrogen bonds in this crystal which link the discrete L-arginine and fluoroborate to form a three-dimensional network.

Crystal Structure of[Cd(pom)_2Cl_2]

Catena-[bis (3-methyl-4-nitropyridine N-oxide ) cadmiumdichloride],[Cd(C_6H_6N_2O_3)_2Cl_2], M_r= 491. 56, monoclinic , P2_1, a= 3. 799 (3), b= 29. 231 ( 9),c=7. 679(5) A, β=100. 19(6)°, V=839. 4 A￣3, Z=2, D_c= 1. 94 g/cm￣3, λ(MoKa)= 0. 71069 A, F(000) =484, P(MoKa) = 16. 5 cm￣(-1), final R=0. 038 for 1202 Observed reflections, T= 296K. The Cd atom is octahedrally coordinated by two O atoms from the trans 3-methyl-4-nitropyridine N-oxide (pom) ligands in the axial positions and four Cl atoms lying in the equatorial plane. The coordination octahedra form chains along the short a axis by edge sharing through the Cl atoms.

Salt-inclusion chalcogenides:Double functional moieties design strategy toward excellent nonlinear optical materials

Nonlinear optical(NLO)material are of great importance in converting the frequency to extend the laser spectrum in mid-and far-infrared(IR)regions where lasers operate poorly or are unavailable.However,the contradiction between large second-harmonic generation(SHG)intensity and wide band gap(E_(g))is a long-standing problem for IR NLO materials.To address the issue,metal chalcogenides have been successfully synthesized and developed excellent optical properties in the past few decades.As a newly discovered category of chalcogenides,salt-inclusion chalcogenides with distinctive structures and brilliant performances have been placed great expecta-tions to be a novel problem-solving.In this review,52 compounds in this thriving family are categorized via dimensions of host and guest parts,further discussing the relationships between their structures and NLO properties,as well as future perspectives of this family.

Nd:Bi_(2)WO_(6)/ZnS纳米复合材料的制备及其光学性能研究

采用简易的化学溶液法结合采用外延生长技术制备Nd:Bi_(2)WO_(6)/ZnS掺杂纳米复合材料。详细地研究了Nd:Bi_(2)WO_(6)/ZnS纳米复合材料的结构、光谱性质和光学性能。通过掺杂的策略,调控了Bi_(2)WO_(6)/ZnS复合结构的光学带隙调控,优化了样品对可见光的利用。当掺杂浓度为5 at%时,样品的禁带宽度最小,对可见光的吸收能力最强,此时产物的光致发光性能最低。

基于含氮衍生物和羧酸的Co(Ⅱ)配合物的合成、结构及磁学、荧光性质

利用水热合成法合成了2种新型的金属有机配合物{[Co(Hbmp)_(2)(H_(2)O)·TFBDC}(1)和{[Co(Hbmp)(TDC)(H_(2)O)]}n(2)(Hbmp为2-(2-苯并咪唑基)-6-甲基吡啶,H2TFBDC为四氟对苯二甲酸,H2TDC为2,5-噻吩二甲酸),利用X射线单晶衍射、X射线粉末衍射、元素分析和红外光谱等方法对其结构进行表征.结果表明,配合物1的晶系是斜方晶系,Fddd空间群,中心离子Co(Ⅱ)为三角双锥构型,晶胞参数为a=1.47278(11)nm,b=2.9178(3)nm,c=3.0274(2)nm.配合物2的晶系是单斜晶系,C2/c空间群,中心离子Co(Ⅱ)为八面体构型,晶胞参数为a=1.77753(17)nm,b=1.84660(17)nm,c=1.33365(12)nm.零维结构的配合物1通过丰富的C—H…O、C—H…F、N-H…O、O—H…O氢键作用力形成三维超分子网状结构.配合物2则是利用羧酸的2种配位模式,将相邻的金属Co(Ⅱ)连接形成了一维链状结构,并借助于丰富的氢键作用力,也拓展成为了三维超分子的网状结构.利用紫外漫反射光谱分析,得到1的E_(g)值为2.65 eV,2的E_(g)值为2.85 eV,证明这2种配合物均是潜在的半导体材料.在1000 Oe的磁场作用下,在2~300 K之间研究了2个配合物的磁性,将测试的变温磁化率数据进行居里外斯拟合,得到居里外斯温度分别为-5.13 K和-5.84 K,证明了这2种配合物存在反铁磁相互作用.