Syntheses, Crystal Structures and NMR of Two Molybdenum Complexes with 2,3-Dihydroxynaphthalene

Two complexes [H3N(CH2)2NH2]2[MoO2(C10H8O2)2] (1) and (C7H10N2)2- [MoO2(C10H8O2)2] (2) were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2(C10H8O2)2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.     

Syntheses,Structures, and Reactivities of Two Chalcogen‐Stabilized Carbones

Electronic effects on the central carbon atom of carbone, generated by the replacement of the S^IV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph₂E, E=S or Se), were investigated. The carbones Ph₂E→C←SPh₂(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor.     

Syntheses and Crystal Structures of Three Palladium（Ⅱ） Complexes with Isonitrosobenzoylacetoneimine Ligand

Three palladium (II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd (p‐CH₃C₆H₄IBI)₂ (1), Pd (C₆H₅IBI)₂ (2) and Pd₂Cl₂ (C₆H₅CH₂IBI)₂ · CHCl₃ (3), were prepared and characterized by IR, Raman and X‐ray diffraction studies. The geometries around the palladium atoms in the complexes 1 and 2 are distorted trans‐PdN₄ square planes, and the Schiff base ligands RIBI^? are coordinated through their oximo‐nitrogen atoms and imino‐nitrogen atoms. The week Pd…H? C agostic interactions [Pd…H = 0.2764 nm] complete the hexacoordinate environment around palladium in the complex 1. The octahedral deformation of the classical square planar environment of the Pd atom is due to the week Pd…O (1b) interactions [Pd? O (1b) = 0.3157 (9) nm] in the complex 2. The complex 3 is a first example of binuclear complex with isonitrosoketoimine ligands, in which one of oximo groups is coordinated through oximo‐nitrogen and oximo‐oxygen atoms.     

Syntheses and Crystal Structures of Three Palladium(II) Complexes with Isonitrosobenzoylacetoneimine Ligand

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Syntheses, Crystal Structures and Antitumor Activities of Two Nicotinamides

Two nicotinamides have been synthesized by coupling aromatic amines with equimolar quantities of substituted nicotinic acids. Their structures have been determined by X-ray single-crystal diffraction. Compound 1, 6-chloro-N-(4-fluorophenyl)nicotinamide, crystallizes in the triclinic space group Pī with a = 4.2188(8) , b = 5.0687(10), c = 25.956(5), α = 86.38(3), β = 87.75(3), γ = 83.20(3)°, V = 549.75(19) 3 and Z = 2. Compound 2, N-(quinolin-3-yl)nico- tinamide, crystallizes in the monoclinic space group P21 with a = 8.5100(17), b = 6.4230(13), c = 11.620(2) , β = 110.39(3)°, V = 595.3(2) 3 and Z = 2. The cytotoxic activities of the two nicotinamides against five human tumor cell lines were tested in vitro. The results indicated that they showed a wide range of antitumor activities.     

Syntheses and Crystal Structures of Pyrazoline Derivants

SNNHNH2 OSSNNHNH2 OS1 INTRODUCTION Pyrazoline derivatives, used as carrier transporting as well as emitting materials[1], have been widely investigated in many areas due to their blue light emission with high quantum yield[2～5], ready acces- sibility and easy processability. 1,3,5-Triaryl-2-pyrazo- lines are reported as the hole transporting or emitting Scheme 1N NN SEtOHmaterials in organic EL devices[6～8]. However, ben- zothiazoyl pyrazolinederivatives containing aro…     

Syntheses,Structures, and Comprehensive NMR Spectroscopic Investigations of Hetero‐Chalcogenidometallates: The Right Mix toward Multinary Complexes

Library of semiconductors : Mixtures of binary chalcogenidostannate anions in protic solution show statistic chalcogenide exchange (see scheme), which is examined by comprehensive NMR investigations, DFT calculations and chemical reactions. A simple approach is provided to generate a library of semiconductor compounds with finely tuned opto‐electronic properties.

     

Syntheses and Crystal Structures of 4,4‘—Diformyl—diphenoxyethane and 4,4’,4‘’—Triformyl—triphenoxytriethylamine

Two title compounds, 4,4'-diformyl-diphenoxyethane (compound 1, C16H14O4)and 4,4',4'-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris2-chloroethylamine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ', = 105.823(6)o, V = 675.7(2)'3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, (MoK = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ', = 99.505(1)°, V = 2383.5(3) '3, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, (MoK = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 dialdehyde is located at the crystallographic inversion center nearby the midpoint of C8-C8A single bond. The three chains in the molecule of compound 2 trialdehyde are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.     

Syntheses, Crystal Structures and Electrochemical Properties of Two Molybdophosphates

Two molybdophosphate compounds,[Ni(bim)3]2[H2P2Mo5O23]·2H2O 1 and [Zn(bpy)2]2[Zn(bpy)(H2O)]2Zn[Mo6O12(OH)3(HPO4)4]2·9H2O 2 (bim = 2,2'-biimidazole,bpy = 2,2'-dipyridyl),have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TG,and IR. The single-crystal X-ray analysis exhibits that 1 consists of one [H2P2Mo5O23]4-,two [Ni(bim)3]2+ cations and two lattice water molecules,while 2 is constructed from one sandwich-type [ZnP4Mo6] anion modified by four Zn-bpy complexes and nine lattice water molecules. The electrochemical behaviors of compounds 1 and 2 have been studied in detail based on solid bulk modified carbon paste electrodes of compound (CPEs).     

铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂]（1）,[Cu（htba）（2,2''-bipy）]（htba）（2）和[Cu（htba）₂（4,4''-bipy）]（3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

一例夹心型含锰铋钨酸盐的合成、结构及磁学性质

在水相中合成了一例新的夹心型含锰铋钨酸盐Na₉H[（Mn （H₂O）₃）₂（Mn （H₂O）₂）（WO₂）（BiW₉O₃₃）₂]·30H₂O （1）。通过元素分析、紫外光谱、红外光谱、粉末X射线衍射、单晶X射线衍射和热重分析对其进行了结构表征。单晶结构分析表明化合物1中的阴离子是由2个三缺位Keggin型β-B-[BiW₉O₃₃]^9-阴离子内、外连接2个[（Mn （H₂O）₂）_0.5（WO₂）_0.5]²⁺配阳离子和2个[Mn （H₂O）₃]²⁺亚单元组成。磁学性质研究表明在化合物1中锰离子之间存在反铁磁耦合作用。     

铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂] （1）,[Cu（htba）（2,2''-bipy）]（htba） （2）和[Cu（htba）₂（4,4''-bipy）] （3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

Syntheses and Structures of Xenon Trioxide Alkylnitrile Adducts

The potent oxidizer and highly shock‐sensitive binary noble‐gas oxide XeO₃ interacts with CH₃CN and CH₃CH₂CN to form O₃XeNCCH₃, O₃Xe(NCCH₃)₂, O₃XeNCCH₂CH₃, and O₃Xe(NCCH₂CH₃)₂. Their low‐temperature single‐crystal X‐ray structures show that the xenon atoms are consistently coordinated to three donor atoms, which results in pseudo‐octahedral environments around the xenon atoms. The adduct series provides the first examples of a neutral xenon oxide bound to nitrogen bases. Raman frequency shifts and Xe?N bond lengths are consistent with complex formation. Energy‐minimized gas‐phase geometries and vibrational frequencies were obtained for the model compounds O₃Xe(NCCH₃)_n (n=1–3) and O₃Xe(NCCH₃)_n?[O₃Xe(NCCH₃)₂]₂ (n=1, 2). Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses were carried out to further probe the nature of the bonding in these adducts.     

Syntheses, Crystal Structures and Characterization of Layered and Layer-pillared Zinc Arsonates

Two zinc arsonate coordination polymers, Zn(4-apa)·H2O (1, 4-apaH2 = 4-amino- phenylarsonatic acid) and Zn(4-apa) (2), have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c with a = 23.056(5), b = 5.4224(11), c = 15.027(3) , β = 121.22(3)°, V = 1606.6(6) ?3, Dc = 2.468 g·cm-3, F(000) = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I > 2σ(I). For 2: monoclinic, space group P21/c with a = 8.7852(18), b = 9.2744(19), c = 9.752(2) , β = 103.45(3)°, V = 772.7(3)3, Dc = 2.410 g·cm-3, F(000) = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I > 2σ(I). The structure of 1 shows a two-dimensional (4,4)-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic (4-82)-networks are joined by the phenyl-linkers.     

Syntheses, Crystal Structures and Properties of Two Lanthanide Selenite-carboxylate Compounds

Two lanthanide selenite-carboxylate （LSC） compounds, namely, [Ln8（SeO3）4（2,6- pdc）8（H2O）10]·2H2O （Ln = Pr 1, Sm 2; 2,6-pdcH2 = pyridine-2,6-dicarboxylic acid） have been hydrothermally synthesized and structurally characterized. Both compounds possess two-dimensional layer structures constructed by Ln8（SeO3）4（2,6-pdc）8（H2O）10 clusters connected to each other via bridging carboxylate groups. The structures are further extended into three-dimensional architectures through extensive inter-layer H-bonding between coordinated water molecules and carboxylate groups. The luminescent properties and thermal stability of both compounds have been investigated.     

Syntheses and Structures of Two Copper Compounds Supported by Octamolybdate

1INTRODUCTION More and more chemists have currently been inte-rested in the transition metal oxides(so-called polyoxometalates)mainly owing to their structural varieties and promising potential applications in catalysis,biology,medicine and materials science[1].Of the various polyoxometalate structures,the most interesting one is the molybdate family with a va-riety of structural polymers including{Mo2},{Mo4},{Mo6},{Mo8}.etc.These molybdate polymersmight act as versatile building blocks …     

Syntheses,Structures, and Reactivities of Two Chalcogen‐Stabilized Carbones

Electronic effects on the central carbon atom of carbone, generated by the replacement of the S^IV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph₂E, E=S or Se), were investigated. The carbones Ph₂E→C←SPh₂(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor.     

系列Ag-Ln配位聚合物的合成、结构及发光性能

采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H_2PDA)和草酸(H_2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1～4是同构的,由2-pzc~-和ox~(2-)连接,而配位聚合物5～9是以3,5-PDA~(2-)和ox~(2-)为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(1)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。     

Orthorhombic HP‐REOF (RE = Pr,Nd, Sm – Gd) – High‐Pressure Syntheses and Single‐Crystal Structures (RE = Nd,Sm, Eu)

High‐pressure modifications of the rare earth oxide fluorides REOF (RE = Pr, Nd, Sm – Gd) were successfully synthesized under conditions of 11 GPa and 1200 °C applying the multianvil high‐pressure/high‐temperature technique. Single crystals of HP‐REOF (RE = Nd, Sm, Eu) were obtained making it possible to analyze the products by means of single‐crystal X‐ray diffraction. The compounds HP‐REOF (RE = Nd, Sm, Eu) crystallize in the orthorhombic α‐PbCl₂‐type structure (space group Pnma, No. 62, Z = 4) with the parameters a = 632.45(3), b = 381.87(2), c = 699.21(3) pm, V = 0.16887(2) nm³, R₁ = 0.0156, and wR₂ = 0.0382 for HP‐NdOF, a = 624.38(3), b = 376.87(2), c = 689.53(4) pm, V = 0.16225(2) nm³, R₁ = 0.0141, and wR₂ = 0.0323 for HP‐SmOF, and a = 620.02(4), b = 374.24(3), c = 686.82(5) pm, V = 0.15937(2) nm³, R₁ = 0.0177, and wR₂ = 0.0288 for HP‐EuOF. Calculations of the bond valence sums clearly showed that the oxygen atoms occupy the tetrahedrally coordinated position, whereas the fluorine atoms are fivefold coordinated in form of distorted square‐pyramids. The crystal structures and properties of HP‐REOF (RE = Nd, Sm, Eu) are discussed and compared to the isostructural phases and the normal‐pressure modifications of REOF (RE = Nd, Sm, Eu). Furthermore, results of investigations by EDX and Raman measurements including quantum mechanical calculations are presented.     

两个镧系配合物的合成, 晶体结构及荧光性质

合成了两个新配合物, [Eu2(Pht)2(HPht)2(Phen)2(H2O)4] (1) and [Gd(3-CNC6H4COO)3(H2O)2]n (2) (Pht2―=dianion of o-phthalic acid; HPht―=mono-anion of o-phthalic acid; Phen=1, 10-phenanthroline; 3-CNC6H4COO=3-cyanobenzoate), 并通过X-射线单晶衍射表征其结构。结果表明,在水热反应条件下1,3-苯二腈水解为3-氰基苯甲酸。配合物2形成了一维链状配合物,而配合物1形成了二聚体。配合物1属三斜晶系,空间群 ,晶胞参数为a = 1.01048(6) nm, b = 1.06755(7) nm, c = 1.19266(8) nm, α = 90.188(3)º, β = 99.526(2)º, γ = 100.981(2)º, V = 1.24479(14) nm3, Z = 1, Dc = 1.861 Mg/m3;配合物2也属三斜晶系,空间群 ,晶胞参数为a = 0.93749(9) nm, b = 1.14943(10) nm, c = 1.27024(11) nm, α = 90.188(3)º, β = 73.788(5)º, γ = 86.757(5)º, V = 1.19389(19) nm3, Z = 2, Dc = 1.757 Mg/m3。用激发和发射光谱研究了配合物1的荧光性质,该化合物能发射很强的红色荧光。