Syntheses,Crystal Structures and Fluorescence Properties of Two Mononuclear Copper(Ⅱ) Compounds

Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.

Synthesis,Crystal Structure and Antifungal Activity of 2-((2-Fluorobenzyl)thio)-5-(pyridin-4-yl)-1,3,4-oxadiazole

The title compound 2-（（2-fluorobenzyl）thio）-5-（pyridin-4-yl）-1,3,4-oxadiazole（C_（14）H_（10）FN_3OS） was synthesized,and its structure was confirmed by ~1H NMR,MS,elemental analyses and X-ray diffraction. It crystallizes in the monoclinic system,space group P21/n with a = 11.541（16）,b = 8.226（12）,c = 13.683（19） ？,β = 94.872（17）o,V = 1294（3） ？~3,Z = 4 and R = 0.0648 for 2198 observed reflections with I 〉 2σ（I）. The preliminary biological test shows that the title compound has good activity against Pythium ultimum with inhibitory to be 100%.

Synthesis,Crystal Structure and Luminescence Study of a New Two-dimensional Mn(Ⅱ)Coordination Polymer

The coordination polymer [Mn2（cipt）2（aic）2]n （cipt = 2-（3-chlorophenyl）-1H- imidazo[4,5-f][1,10]phenanthroline, aic = 5-amino-isophthalic acid） has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P , with a = 11.523（3）, b = 12.162（3）, c = 18.706（5） A^°, β = 81.789（5）°, V = 2455.2（1） A^°3, C54H32Cl2Mn2N10O8, Mr = 1129.68, Z = 2, Dc = 1.528 g/cm3, μ = 0.692 mm^-1, F（000） = 1148, R = 0.064 and wR = 0.145 for 9571 observed reflections （I 〉 2σ（I））. In this polymer, the Mn（II） atoms adopt different coordination modes. The Mn（1） atom is five-coordinated, forming a distorted tetragonal pyramidal geometry. Mn（2） atom is six-coordinated to get a distorted octahedral geometry, which is different from the Mn（1） atom. Each Mn（II） atom is linked by aic ligands with neighboring Mn（II） atoms, forming an infinite one-dimensional （1D） double-chain structure. The existence of N–H…O hydrogen bonding interactions leads the 1D chains to generate a 2D structure. Luminescent properties for the ligand cipt and compound 1 have also been discussed in detail.

Crystal Structure and Magnetic Properties of a Dinuclear Terbium Compound Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2

A dinuclear Tb（Ⅲ） compound, Tb_2（μ_2-anthc）_4（anthc）_2（1,10-phen）_2（1, Hanthc = 9-anthracenecarboxylic acid and 1,10-phen = 1,10-phenanthroline）, was synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1, with a = 12.5061（12）, b = 13.3168（10）, c = 15.0079（12） ？, α = 110.620（7）, β = 102.941（7）, γ = 107.036（7）o, V = 2081.8（3） ？~3, Z = 1, C_（114）H_（70）N_4O_（12）Tb_2, M_r = 2005.58, D_c = 1.600 g/cm^3, μ = 1.759 mm^（-1）, F（000） = 1008, the final R = 0.0294 and w R = 0.0608 for 8900 observed reflections with I 〉 2s（I）. In compound 1, two Tb（Ⅲ） ions are linked by four carboxylate groups of the bridging anthc– ligands to give a dinuclear Tb_2（μ_2-anthc）_4 unit wherein each Tb（III） ion is further capped by a terminal anthc– ligand and a 1,10-phen ligand in a chelating fashion. Detailed direct-current and alternating-current susceptibility measurements showed no slow magnetism relaxation phenomenon was observed for 1.

Solvothermal Synthesis,Crystal Structure and Luminescent Property of a Two-dimensional Lead(Ⅱ) Compound：[Pb(bmzbc)2]n

A two-dimensional coordination polymer, [Pb（bmzbc）2]n（1）（Hbmzbc =4-benzimidazole-1-yl-benzoic acid）, has been synthesized by the solvothermal reaction of Pb（NO3）2 with Hbmzbc at 120 ℃ in ethanol solvent. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the orthorhombic system, space group Pccn, with a = 12.5801（7）, b = 20.0795（11）, c = 9.1830（6） ？, V = 2319.6（2） A^3, Z = 4, C（28）H（18）N4O4Pb, Mr = 681.65, Dc = 1.952 g/cm^3, μ = 7.319 mm^-1, F（000） = 1312, the final R = 0.0336 and wR = 0.0965 for 1699 observed reflection with I 〉 2σ（I）. In 1, the bmzbc^– ligands bridge the Pb（Ⅱ） ions to generate a 2-D sheet with（4, 4） topology. The complex exhibits turquoise photoluminescent emission with a maximum at 480 nm upon excitation at 300 nm.

Synthesis,Crystal Structure and Photoluminescent Property of a Novel Dy^(3+) Coordination Compound Containing Rare(H_2O)_(22) Clusters

A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.

Crystal Structure of Tris(m-nitrobenzoato) Samarium Dihydrate

The crystal structure of [Sm(m-NO2C6H4CO2)3(H2O)2] was determined.Mr=684. 66,triclinic,space group P1.α=11. 408(6),b=12.990(6).c=9.469(3) A,α=104. 84(3),β=92.84,γ=65.31(3)°,V=1229.9(9)A3.Z=2,Dc=1.85g/cm3, F(000)=674,μ=25.1 cm-1,R=0.67.The coordination number of samarium ion is eight.The metal ions are bridged by carboxylato groups to form a polymeric chain structure.The crystal data of [Ho (m-NO2C6H4CO2)3 (H2O)2] were measured:triclinic,space group P1,α=11.368(3) .b=12. 943(3),c=9.443(1) A α=104.92(1),β=92.80(3),γ=65.07(2)°,V=1214.7(4)A 3,Z=2,Dc=1.91 g/cm3.These show that the samarium and holmium cornpounds are isomorphous.

Crystal Structure and Magnetic Properties of a Two-dimensional Compound{(Me2NH2)4[Co(SIP)2]·2(DMF)·3(H2O)}n

A new cobalt（II） compound, {（Me2NH2）4[Co（SIP）2]·2（DMF）·3（H2O）}n（1, H3 SIP =5-sulfoisophthalic acid）, has been synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system,space group P 4 21 m, with a = 14.3080（7）, b = 14.3080（7）, c = 12.1837（9） ?, V = 2494.2（3） ?~3, Z =2, CHNOSCo, Mr = 929.87, Dc = 1.238 g/cm, μ = 0.496 mm, F（000） = 982, flack parameter of 0.007（9）, the final R = 0.0767 and wR = 0.2110 for 2391 observed reflections with I >2σ（I）. The tetrahedral Co（II） ions are linked by carboxylate groups of the 5-sulfoisophthalate ligands to form an anionic two-dimensional（2D） layer displaying a（4,4） square network, which was charge-balanced by the [MeNH] + cations occupying the spaces between the 2D layers. Magnetic properties of 1 have been investigated in detail using direct-current and alternating-current susceptibility measurements.

A Dinuclear Dysprosium-2-quinolinecarboxylate-1,10-Phenanthroline Compound:Crystal Structure and Magnetism

A dinuclear dysprosium（III） compound,[Dy2（μ2-OH）2（QLC）4（1,10-phen）2]·4H2O（1）（QLC-= 2-quinolinecarboxylate and 1,10-phen = 1,10-phenanthroline）,was synthesized and structurally and magnetically characterized.Compound 1 crystallizes in triclinic system,space group P1 with a = 10.9439（3）,b = 11.2823（3）,c = 12.2323（4） ？,α = 107.446（3）,β = 91.700（3）,γ = 91.511（2）°,V = 1439.25（8） A3,Z = 1,C（64）H（50）N8O（14）Dy2,Mr = 1480.12,Dc = 1.708 g/cm3,μ = 2.653 mm-1 and F（000） = 734.The final R = 0.0366 and w R = 0.0736 for 5816 observed reflections with I 〉 2σ（I）.Compound 1 contains the mononuclear [Dy（QLC）2（1,10-phen）] subunit formed from one 1,10-phen and two QLC-ligands chelating Dy（III） ion.Two mononuclear [Dy（QLC）2（1,10-phen）] subunits are bridged by a pair of μ2-OH groups to give a centrosymmetric dinuclear [Dy2（μ2-OH）2（QLC）4（1,10-phen）2] with each Dy（III） ion being eight-coordinated.Detailed susceptibility measurements revealed that compound 1 does not show slow magnetic relaxation under zero direct-current field but exhibits field-induced slow magnetic relaxation under 2 kOe applied field.

Synthesis and Crystal Structure of a New Quaternary Sulfide FeSm6Si2S14

One new quaternary rare-earth sulfide, FeSm6Si2S（14）, has been synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al（3.33）S（14） structure-type, and the AxRE3MQ7 family. Its crystal structure features a 3-D framework constructed by SmS 8 bicapped trigonal prisms, where Fe and Si atoms occupy the octahedral（2a） and tetrahedral（2c） voids, respectively. The FeS 6 octahedra are connected with each other to form a chain along the b direction. FeSm6Si2S（14） represents a new chemical composition among the large family of AxRE3MQ7 compounds. The other related compounds containing transition metal are also discussed.

Synthesis, Crystal Structure and Magnetic Properties of a Cobalt(Ⅱ) Complex with Quinoxaline-substituted Nitronyl Nitroxide Radicals

A new complex with the formula [Co（acac）_2（NITQ）_2]×2CH_2Cl_2 1（acac = acetylacetone, NITQ = 2-（2′-quinoxalinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide）, was synthesized and elucidated structurally as well as magnetically in detail. The crystal belongs to the monoclinic system, space group P2_1/c with a = 9.6896（1）, b = 20.539（4）, c = 12.147（2） ？, β = 93.84（3）°, M_r = 997.65, V = 2412.1（8） ？~3, Z = 2, Dc = 1.374 g/cm, F（000） = 1038, m = 0.635 mm^（-1）, the final R = 0.0539 and w R = 0.1289 for 5998 observed reflections（I 〉 2σ（I））. The Co（Ⅱ） ion is coordinated by two nitrogen atoms of quinoxaline rings from two NITQs and four oxygen atoms from two acac ions to complete a distorted octahedral coordination environment. Compound 1 is further linked into a three-dimensional（3D） supramolecular network by hydrogen-bonding, Cl×××O weak contact and π···π stacking interactions. The magnetic measurements show compound 1 exhibits weak ferromagnetic interactions.

STRUCTURE OF MOLECULAR COMPOUND CRYSTAL A_2B(A =1, 6, 7, 8,-TETRA-PHENYL (3, 4-BENZO)BICYCLO[4, 2, 0]OCTA-7-ENE, B=CIS, CIS-1,2,3,4,-TETRAPHENYLBUTADIENE)

C100H78, (A: C36H28, B: C28H22) Mr = 1279. 74, monoclinic, P21/a, a=17. 282(3), b=10. 669(4), c= 19, 927(3) A , β =102. 99(1)°,V = 3580. 1(2) A3, Z=2, μ(MoKα) = 0. 623cm-1, F(000) = 1356, Dc=1. 187g/cm3, room temperature. The final R=0. 084, Rw = 0. 086 for 1255 independent observed reflections (I≥3σ(I)). Owing to the existence of 1,6,7, 8-Tetraphenyl (3,4-benzo)-bicyclo[4, 2, 0]octa-7-ene(A) , cis, cts-1, 2, 3, 4-Tetraphenylbutadiene (B) in A2B can take the different conformation from the one in the pure B crystal. The reason of the formation of this molecular compound crystal is put forward.

Numerical Simulation of the Multicomponent Mass Transfer during Bridgman Growth of CdZnTe Crystal Using Maxwell-Stefan Diffusion Model

To reveal the complicated mechanism of the multicomponent mass transfer during the growth of ternary compound semiconductors, a numerical model based on Maxwell-Stefan equations was developed to simulate the Bridgman growth of CdZnTe crystal. The Maxwell-Stefan diffusion coefficients in the melt were estimated. Distributions of Zn, Cd, and Te were calculated with variable ampoule traveling rate and diffusion coefficients. The experimental results show that Zn in melt near the growth interface decreases and diffuses from the bulk melt to the growth interface. For Cd, the situation is just the opposite. The coupling effects of Zn and Cd diffusions result in an uphill diffusion of Te at the beginning of the growth. Throughout the growth, the concentration of Te in the melt keeps low near the growth interface but high far from the growth interface. Increasing the ampoule traveling rate will aggravate the segregation of Zn and Cd, and hence deteriorate the uniformity of Te. We also find that not only the diffusion coefficients but also the ratios between them have significant influence on the species diffusions.

Synthesis,Crystal Structure and Photophysical Property of 4-(9-Oxoacridin-10(9H)-yl)Benzonitrile

A purely organic compound, 4-（9-oxoacridin-10（9 H）-yl） benzonitrile（1）, was synthesized and characterized by NMR, UV-Vis, high resolution mass spectrum, and X-ray single-crystal structure analysis. It crystallizes in monoclinic system, space group P21/c with a = 9.7420（2）, b = 10.4967（2）, c = 14.3896（3）A°, β = 104.755（2）°, V = 1422.94（5）, Z = 4, Mr = 296.32, Dc = 1.383 g/cm^3, F（000） = 616, μ = 0.690 mm^–1, GOOF = 1.035, the final R = 0.0370 and w R = 0.1010 for 2649 observed reflections with I 〉 2σ（I）. Compound 1 in tolune exhibits deep blue luminescence with maximum emission peaks at 403 and 419 nm, lifetimes of 3.8 ns and quantum yields of ф = 0.46 at room temperature. The experimental and computational results show that the emission of the compound originates from the acridinone moiety and has π-π＊ character.

PBO fibers/fluorine-containing liquid crystal compound modified cyanate ester wave-transparent laminated composites with excellent mechanical and flame retardance properties

Bisphenol A dicyanate ester resins modified by fluorine-containing liquid crystal compound(LCFE)are applied as polymer matrix(LCFE-BADCy),poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers as rein-forcements,and fluorine/adamantane PBO precursor(pre FABPBO)as interfacial compatibilizer to prepare the corresponding PBO fibers/FABPBO/LCFE-BADCy wave-transparent laminated composites.LCFE could improve the order degree of BADCy cured network,in favor of enhancing the wave-transparent perfor-mance,mechanical properties,and intrinsic thermal conductivity.The dielectric constant and dielectric loss of PBO fibers/FABPBO/LCFE-BADCy composites are highly temperature(25–200℃)and frequency(10^(4)–10^(7) Hz and 8.2–12.4 GHz)stable with the value of 2.49 and 0.003 under 10^(6) Hz at 25℃,and the corresponding wave transmission efficiency is 95.0%,higher than that of 92.5%for PBO fibers/BADCy com-posites.The interlamellar shear strength and flexural strength are respectively 50.7 MPa and 682.5 MPa,38.1%and 16.2%higher than those of PBO fibers/BADCy composites.Besides,the volume resistivity,breakdown voltage,heat resistance index,glass transition temperature,flame retardant grade,and ul-timate oxygen index of PBO fibers/FABPBO/LCFE-BADCy composites are respectively 5.3×10^(15)Ωcm,29.75 kV/mm,217.2℃,245.7℃,V-1 grade,and 33.6%,expected to be performed as a new generation of“lightweight/loading/wave-transparent”electromagnetic window materials in advanced military weapons and civil communication base station.

Studies on solid state reactions of coordination compounds——XLⅦ.Solid state syntheses and crystal structures of cluster compounds {Cu_3MoS_3I}(PPh_3)_3S and {Cu_3WS_3Br} (PPh_3)_3S

Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state produced four mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which (1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic, space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°, Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c= 20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observed reflections).The results of the structure determination showed that the central units of the two cubane- like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter- nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.

Synthesis and photoswitching properties of azobenzene liquid crystals with a pentafluorobenzene terminal

The fluorine-substituted benzoate ester rod-shaped liquid crystals containing an azobenzene side chain linked with terminal double bonds were synthesized and characterized.The mesophase and photoswitching properties were determined by polarizing optical microscopy（POM）,differential scanning calorimetry（DSC） and UV-visible spectrometry.The rod-shaped compound 4a having an odd number of carbon atoms in the alkyl chains exhibits nematic phase and SmA type phase whereas compound 4b having an even number of carbon atoms showed only nematic phase.Both fluorinecontaining compounds 4c and 4d showed only SmA type phases.The photoswitching properties of these compounds showed a rate of trans to cis isomerization ranging 19-20 s,whereas reverse process took around 230 min in solution.These materials may be ideal in the field of optically rewritable applications where both on and off rates should be crucial.

Structure, magnetic properties, and thermal stability of Sm(1-x)Tm_xCo_5compounds

Structure, magnetic properties, and thermal stability of ternary Sm1-xTmxCo5 compounds were studied via X-ray diffraction（XRD）, thermal magnetic analysis（TMA）, and magnetic measurements. XRD results show that all the compounds have a main phase of hexagonal CaCu5-type crystal structure with small amount of impurity phases; increasing Tm content is associated with contraction of the hexagonal unit cell in the direction of the c axis and expansion of the a and b parameters. TMA results indicate that the Curie temperature（TC） of Sm1-xTmxCo5 compounds gets higher with the increase in Tm content.Magnetic measurements show that both the magnetic anisotropy field（HA） and the magnetization at an applied field of 7 T（M7 T） decrease with the increase of Tm content. However, the thermal stability of both the HAand M7 Tof all the Tm doped compounds is remarkably improved compared with that of the pure SmCo5 compound, leading to the result that both the M7 Tand HAof Sm0.8Tm0.2Co5 .2are higher than those of SmCo5 compound at 473 K, which indicates the good potential of Tm doped compound in the practical applications at elevated temperature.