Organometallic Gold（Ⅲ） Derivatives with Anionic Oxygen Ligands-mononuclear Hydroxo,Alkoxo, and Acetato Complexes： Synthesis and Spectral Study

A variety of gold（Ⅲ） adducts having a-ligated oxygen-donor ligands have been prepared from [Au（ppy）Cl2]（ppy.phenylpyridine）（1） either by partial or total replacement of the chloride ions. The new species comprise hydroxo-[Au（ppy）（OH）Cl]（2）, and [Au（ppy）（OH）2]（3）, oxo-[Au2（ppy）2（μ-O）2]（4）, acetate-[Au（ppy）（O2CMe2）] （5）, and alkoxo complexes-[Au（ppy）（OR）Cl]（6, 7） and [Au（ppy）（OR）2]（8--10）（R=Me, 6 and 8; Et, 7 and 9; Pr, 10）. The dihydroxo and the oxo complexes can be interconverted by refluxing the former in anhydrous THF and the latter in water. The hydroxides 2 and 3 and the acetato complex 5 undergo σ-ligand metathesis in ROH solution（R=Me, Et or Pr） to give the corresponding alkoxides.     

A twin-axial[5]pseudorotaxane based on cucurbit[8]uril and a-cyclodextrin

A twin-axial hetero[5]pseudorotaxane was constructed based on 1-hexyl-4,40-bipyridinium guest 1 and cucurbit[8]uril（CB[8]）and a-cyclodextrin（a-CD）.In its structure,CB[8]included two bipyridinium units to realize the twin-axial mode,and the hexyl chain was threaded into the cavity of a-CD.The[5]pseudorotaxane contains two types of macrocyclic hosts while the single axial and twin axial modes co-exist in its structure.The transformation of[5]pseudorotaxane could be realized by the addition of acid and 2,6-dihydroxynaphthalene（HN）.     

Isomers and [2,3]-Sila-wittig Rearrangement of [（Allyloxy）silyl]lithium Silylenoid in the Gas Phase and THF Solvent

Theoretical calculations of the [2,3]-sila-wittig rearrangement of isomers of [（allyloxy）silyl]lithium （C3H5O）HzSiLi have been performed in the gas phase and THF solvent using the G3MP2B3 method. Seven isomers of silylenoid （C3H5O）H2SiLi, 1-7, are found. The [2,3]-silawittig rearrangement paths are followed using two isomers, 2 and 4, to yield the transition states as well as the products. In the transition state, the silicon center functions as a nucleophile and the aUyl as an electrophile. The interaction between the silicon and allylic sites leads to the formation of SiC（3） bond and the break of O-C（1） bond. Finally, the （allylsilyl）oxylithium （C3H5）H2SiOLi is obtained. The rearrangement paths are confirmed by the intrinsic reaction coordinate （IRC） calculations. The rearrangement mechanisms of reactions of 2 and 4 are similar, and the latter reaction is more favored in the gas phase and THF solvent. Also, the solvent effects are analyzed in this work.     

Syntheses,Structures and Properties of Three Transition Metal Coordination Polymers Based on Semi-rigid 3-Pyridylnicotinamide and S/N-Containing Dicarboxylate Mixed Ligands

Three new coordination complexes, [Co（L）（ADTZ）]·H2O（1）, [Cd（L）（ADTZ）]·H2O（2） and [Zn（L）（ADTZ）]·H2O（3）[L=3-pyridylnicotinamide, H2ADTZ=2,5-（s-acetic acid）dimercapto-1,3,4-thiadiazole], were synthesized under hydrothermal conditions. These complexes were structurally characterized by single-crystal X-ray diffraction analysis and further characterized by infrared spectroscopy（IR）, powder X-ray diffraction （PXRD） and thermogravimetric analysis（TGA）. Complexes 1-3 exhibit the similar 2D double-layer networks based on 1D [M-L], zigzag chains and 1D [M-ADTZ]2n double-chains with different distances between metal ions and with various conformations of ADTZ anions. In complexes 1 and 3, the 2D sheets are extended into a 3D supramolecular frameworks by hydrogen bonding interactions. The subtle effects of the central metal atoms on the structures of the title coordination polymers were discussed. The electrochemical properties of complex 1 and luminescent properties of complexes 2 and 3 were investigated. In addition, complexes 1-3 exhibit photocatalytic activity for dye methylene blue degradation under UV light and show good stability toward photoca- talysis.     

Theoretical Study of the Structure, Mechanism of Detonation Initiation and Stability of Transition Metal Carbohydrazide Nitrates

The geometric structure, mechanism of detonation initiation and stability of transition metal carbohydrazide （CHZ） nitrates are investigated via density functional theory. The obtained results show that the Heyd-Scuseria-Ernzerhof （HSE） functional yields the most accurate geometry. The initiating reaction of detonation in [Mn（CHZ）3]（NO3）2 and [Zn（CHZ）3]（NO3）2 is the formation of NO3 radicals. The calculated heat of formation and energy gap predict that the Mn and Zn complexes, which have the half-filled （3d5） and full-filled （3d10） electron configurations for the transition metal ions, respectively are more stable than the Co, Ni and Cu complexes. This indicates that the electron configuration of transition metal ion plays an important role in the stabilities of these energetic complexes.     

Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

A series of new iridium complexes, IrCl（COD）（TMOPP） （1） [COD=1,5-cyclooctadiene, TMOPP=tris（4- methoxyphenyl）phosphine], IrCl（COD）（TFMPP） （2） [TFMPP = tris（4-trifluoromethylphenyl）phosphine], IrCl（COD）（BDNA） （3） [BDNA= 1,8-bis（diphenylphosphinomethyl）naphthalene], IrCl（COD）（BISBI） （4） [BISBI= 2,2＇-bis（diphenylphosphinomethyl）biphenyl] and IrCl（COD）（BDPB） （5） [BDPB= 1,2-bis（diphenylphosphinomethyl）benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl（COD）（DPPM） （6） [DPPM = bis（diphenylphosphino）methane], IrCl（COD）（DPPE） （7） [DPPE= 1,2-bis（diphenylphosphino）ethane], IrCl（COD）（DPPP） （8） [DPPP=1,3-bis（diphenylphosphino）propane] and IrCl（COD）（TPP） （9） [TPP=triphenylphosphine], were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of C-O bond in avermectin to give a byproduct avermectin aglycon.     

几个金属卤素簇的合成与性能研究

The hydrothermal reaction of CuBr2 and CuBr with phen·H2O （phen= 1,10-phenanthroline） in a molar ratio of 1：1：1.5 gave birth to the first copper-halo cationic cluster [Cu2^Ⅱ Cu2^Br4 （phen）4 ] ^2＋（1） with tetranuclear anionic cluster [Cu4Br6]^2-. Changing the precursors or their molar ratios, two mononuclear complexes [Cu（phen）2Br]Br·H2O （2） and [Ni（phen）3][CuCl2]2 （3） as well as two unusual copper-halo chains found in polymers [Cu2Br2（phen）]∞ （4） and [Cu^ⅡCu3^ⅠBr2Ⅰ3 （phen）2 ]∞ （5） were obtained. The （Cu2Br2）∞ chain of 4 looks like a linearar ray of hexagons based on fused Cu3Br3 units, and the linear （Cu3Ⅰ3Br^-）∞ chain of 5 is an alternate combination of the rhombic Cu2I2 cores and the Cu4I4Br2^2- units. In addition, the hydrothermal reaction of CuBr2 with NA（NA=nicotinic acid） or INA （INA =isonicotinic acid） resulted in the syntheses of two compounds [CuBr（NA）] （6） and [CuBr（INA）]∞（7） containing staircase chain. Among them the third-order non-linear optical properties of 2, 5, 6 and 7 were investigated and all exhibit the reverse saturable absorption （α2〉0） and self-defocusing performance （n2〈0）.     

Novel Donor-Acceptor Copolymers Based on Dithienosilole and Ketone Modified Thieno[3,4-b]thiophene for Photovoltaic Application

Two novel donor-acceptor （D-A） copolymers containing dithienosilole （DTS） donor unit and ketone modified thieno[3,4-b]thiophene （TT） acceptor unit, namely, poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2-b：2＇,Y-d]silole-5,5＇-diyl- alt-l-（thieno[3,4-b]thiophen-2-yl）-2-ethylhexan-l-one} （PDTSTT） and poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2- b：2＇,3＇-d]silole-5,5＇-diyl-alt- 1-（4,6-bis（4-ethylhexylthien-2-yl）thieno[3,4-b]thiophen-2-yl）-2-ethylhexan- 1-one} （PD- TSDTTT）, were synthesized for the application in polymer solar cells （PSCs）, and the effects of thiophene bridge on the structural geometry and photovoiltaie performance have been investigated. The polymer PDTSTT and PDTSDTTT have the electrochemical bandgaps of 1.54 and 2.02 eV, together with low-lying HOMO energy levels of-5.47 and -5.37 eV, respectively. Molecular geometry simulation result shows that compared with PDTSTT, the insertion of thiophene bridge in PDTSDTTT can well relieve the steric hindrance between the TT and DTS unit, as confirmed by the reduced dihedral angle between DTS and DTTT unit. Under the illumination of AM 1.5G, 100 mW/cm2, the PSC based on PDTSDTTT/PC61BM （1 ： 1, w ： w） demonstrates a power conversion efficiency of 1.0%, which is significantly improved in comparison with the device based on PDTSTT/PC61BM （1 ： 2, w ： w） under the same experimental condition. This is because the enhanced planarity and increased effective conjugation of the main chain in PDTSDTTT promote the more favorable morphology for charge transportation, although PDTSTT possesses the broader absorption band than PDTSDTTT.     

Investigation of the Spin Crossover Complex [Fe（bapbpy）（NCS）_2 ] in Its Low-spin and Highspin State by DFT/TD-DFT/BS-DFT Calculations

The spin crossover（SCO） compound [Fe（bapbpy）（NCS）2],where bapbpy contains two fused N,N-bis（2-pyridyl）amines,has been studied by DFT/TD-DFT/BS-DFT methods.Several density functionals and basis sets were used in the calculation to obtain optimized geometries of the compound in the low-（LS） and high-spin（HS） states.The vibrational modes and IR spectra,spin splitting energies,excited states and UV/Vis absorption spectra were obtained.The structural parameters of the calculated isolated complex are in good agreement with the X-ray data.We investigate three dimers of [Fe（bapbpy）（NCS）2] complex for their magnetic properties.It has been found that the complex（1,3） has ferromagnetic character while the others are antiferromagnetic in nature by using a broken symmetry approach in the DFT framework（BS-DFT） with support from the coupling constant values（J） and spin density plots.     

Characterization, Crystal Structure and Initial DNA Binding Interaction of Two Cu（Ⅱ） Complexes with 4,5-Diazafluoren-9-one

Two new complexes [Cu（dafo）2（en）]（ClO4）2·2H2O （en=NH2CH2CH2NH2） 1 and [Cu（dafo）2（dap）]（ClO4）2·2H2O [dap=NH2CH2CH（CH3）NH2] 2 （dafo=4,5-diazafluoren-9-one） have been synthesized and characterized by elemental analysis, IR and UV spectra. Meanwhile, the complex 1 has been characterized by single crystal X-ray diffraction analysis. The initial DNA binding interactions of the complexes 1 and 2 have been investigated by UV spectra, emission spectra and cyclic voltammogram. Concluding the results of three methods used to measure the interaction of complexes 1 and 2 with DNA, the action mode of the two complexes with DNA is intercalation, and character of ligands and steric effect may affect the interaction of the complexes with DNA.     

Theoretical Investigation on the Absorption and Emission Properties of the Three Isomers of Bis（thiocyanato）（2,2^1-bipyridyl）platinum（ll）

This paper presents a Density Functional or Time Dependent Density Functional （DFT/TDDFT） study of the molecular and electronic structures, optical absorption and emission spectra of three linkage isomers： bis（isothiocyanato-S）（2,2^1-bipyridyl） platinum（II） （[Pt（SCN）2（bpy）]）, （isothiocyanato-S）（thiocyanato-N）-（2,2^1-bipy- ridyl） platinum（II） （[Pt（SCN）（NCS）（bpy）]）, and bis（thiocyanato-N）（2,2^1）-bipyridyl）platinum（II） （[Pt（NCS）2（bpy）]）, in which different coordination ligands based on the N- and S-coordination of the thiocyanato ligands control the luminescent color. The electronic structures were studied using the B3LYP functional. Optimized geometries Were compared to the experimentally observed structures. TDDFT calculation was carded out to investigate the excited singlet and triplet states. Calculations have been performed both in vacuo and in solvents, using a polarized continuum model （PCM） to account for solute-solvent interactions. Inclusion of the solvent led to a significant energy change, and as a consequence, the computed spectrum calculated in the presence of the solvent was in good agree- ment with the experimental determinations. The first two absorptions were found to originate from mixed plati- num-SCN （or NSC） to bipyridyl-n＊ transitions rather than pure metal-to-ligand-charge-transfer （MLCT） transitions, whereas the higher-energy bands arose from intraligand n→π＊ transitions. The stretching frequencies of C≡N have been calculated both in the ground and excited states, which are relative to the charge transition during the excitation. In addition, different sizes of basis sets were also discussed in this paper.     

Synthesis and Characterization of Two [2]Catenanes Based on Phenylene-diacetylene Crown Ethers

Two charged donor-acceptor [2]catenanes were synthesized by the cyclization of the π-acceptor 1,1 ＇-[1, 4-phenylenebis-（methylene）]bis（4,4＇-bipyridinium）bis（hexafluorophosphate）（2） and bis（bromomethyl）benzene with the templates of the π-donor phenylene-diacetylene crown ethers la and lb in the yields of 31%, 35%, respectively. The mass spectra, 1H and 13C NMR spectra confirm that the phenylene-diacetylene crown ethers, with a nonaromatic ~r-system, successfully template the cyclization of CBPQT4＋. The X-ray crystallography analysis shows that the CBPQT4＋ ring encircles around the phenylene motif of the crown ethers, leaving the 1,3-butadiyne fragment out of the cavity of CBPQT4＋ ring. The mechanically interlocked structure of [2]catenanes was stabilized by the cooperative effects of π-stacking and hydrogen bonding interactions.     

QSAR Study on Some N-[5-（2-Furanyl）-2-methyl- 4-oxo-4H-thieno[2,3-d]pyrimidin-3-yl]-carboxamide and 3-Substituted-5-（2-furanyl）-2-methyl-3H-thieno- [2,3-d]pyrimidin-4-ones Using Three-dimensional Holographic Vector of Atomic Interaction Field

Study on the quantitative structure-activity relationship （QSAR） of 26 compounds, N-[5-（2-furanyl）-2-methyl-4-oxo-4H-thieno[2,3-d]pyrimidin-3-yl]-carboxamide and 3-substituted- 5-（2-furanyl）-2-methyl-3H-thieno[2,3-d]pyrimidin-4-ones, with three-dimensional holographic vector of atomic interaction field （3D-HoVAIF） was carried out. SMR-PLS QSAR models have been created and good correlation coefficients and cross-validated correlation coefficients were obtained. The result shows that the models have good prediction capability and favorable stability and the 3D-HoVAIF is applicable to the molecular structural characterization and biological activity prediction.     

[Cp2Ln(m-h1:h2-OC(SR)=CPh2 )]2 的合成和表征

[Cp2Ln（μ-SR）]2 was reacted with Ph2C=C=O to yield ketene mono-insertion products [Cp2Ln（μ-η1：η2-OC（SR）=CPh2）]2 [R=Bn, Ln=Yb （1）, Er （2）, Y （3） and R--Ph, Ln=Yb （4）], indicating that the reactions of organolanthanide thiolates with ketenes are independent of the nature of the thiolate ligand and the ketene as well as the reaction condition. These reactions could provide an efficient method for the synthesis of organolanthanide complexes with the a-thiolate-substituted enolate ligand. All these complexes were characterized by elemental analysis and spectroscopic properties and the structure of complex 1 was determined through X-ray single crystal diffraction analysis.     

Synthesis, Characterization and Properties of Tri-substitute Potassium Salt of Trinitrophloroglucinol

The title complex [K3（TNPG）·（H2O）2]n was synthesized by the reaction of the aqueous solutions of trinitrophlomglucinol （TNPG） with KHCO3. The complex was characterized by elemental analysis and FTIR spectroscopy, and its single crystal structure was determined by X-ray diffraction analysis. The structural analysis demonstrates that two different coordination modes of K cations [K（1） and K（2）] are around TNPG^3- anions in complex [Ka（TNPG）·（H2O）2]n, where the coordination numbers are eight. All K atoms coordinate with O atoms of phenolic hydroxyl group and nitro-group simultaneously. The thermolysis of the [Ka（TNPG） · （H2O）2]n has been investigated by using differential scanning calorimetry （DSC） and thermogravimetry-derivative thermogravimetry （TG-DTG） at a heating rate of 10 ℃/min. The thermal decomposition processes of the title complex were comprised of one endothermic dehydration stage and one exothermic decomposition stage in 270-320℃, and the final decomposition residue contained KNC. Impact and friction sensitivity results of the complex revealed its sensitive nature towards mechanical stimuli. The experiments verified that the complex has some characteristics of explosive.     

SYNTHESIS AND PROPERTIES OF COPOLYMERS CONTAINING CUCURBIT[6]URIL-BASED PSEUDOROTAXANE STRUCTURE

Novel copolymers based on acrylamide（AM）and complex pseudorotaxane monomer N’-（3-vinylbenzyl）-1,4- diaminobutane dihydrochloride with cucurbit[6]uril（CB[6]）（3VBCB）were prepared via free-radical polymerization in aqueous solution,and characterized by ¹H-NMR,FT-IR,elemental analysis and static light scattering.The compositions of the copolymers（PAM3VBCB）with pseudorotaxane units were determined by ¹H-NMR and elemental analysis.Thermal properties of the copolymers were studied by TGA,and the effects of the copolymer concentration and pH on the average hydrodynamic radius（R_h）of the copolymer molecules were studied by dynamic light scattering（DLS）.The experiment data show that CB[6]beads are localized on 1,4-diaminobutane units in side chains of the copolymers.TGA results show that thermal stability of the copolymer increases with increasing the content of pseudorotaxane unit because of the enhanced rigidity and the bulky steric hindrance of 3VBCB in side chains of PAM3VBCB.DLS data show that the average hydrodynamic radius of copolymer molecules increases with the increase in the copolymer concentration,and both the pH and electrical conductivity of PAM3VBCB solutions demonstrate an acute change with addition of NaOH because of CB[6] dethreading from the side chains of PAM3VBCB.CB[6]threading and dethreading of PAM3VBCB could be controlled by addition of BaCl₂ and Na₂SO₄     

Synthesis,Bioactivity and Crystal Structure Analysis of 2-（Benzo [d]isothiazol-3-yloxy）-N-（3-cyano-l-（4- fluorophenyl）-lH-pyrazol-5-yl） Acetamide

A novel benzisothiazolin-3-one derivative, 2-（benzo[d]isothiazol-3-yloxy）-N-（3- cyano-l-（4-fluorophenyl）-lH-pyrazol-5-yl） acetamide （8）, was synthesized from the initial compound benzo[d]isothiazol-3（2H）-one （BIT） 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed tile target compound exhibited a good anti-microbial activity.     

Theoretical Investigations on the Electronic and Optical Properties of Luminescent Poly（alkylthiophene-co-pyridine）

Quantum-chemical techniques were applied to investigate a series of conjugated polymers： poly（3-octylthien-2,5-ylene-co-pyrid-2,6-ylene） （pl）, poly[pyrid-2,6-ylenebis（3-octylthien-2,5-ylene）] （p2） and poly[pyrid-2,5-ylenebis（3-octylthien-2,5-ylene）] （p3） comprising alternating n-excessive 3-alkylthiophene and n-deficient meta- or para-linked pyridine moieties. Their ground state and excited state structures were optimized with density functional theory B3LYP method, and the optical properties were calculated by the time-dependent density functional theory （TD-DFT） and ZINDO/S methods. Their HOMO-LUMO gaps （An-L）, the lowest excitation energies （Eex）, ionization potentials （IP） and electron affinities （EA） were obtained by extrapolating those of the polymers to the inverse chain length equal to zero （1/n=0）. The calculated results showed that the decrease of pyridylene content increased the HOMO level and decreased the LUMO level while the para-linkage further contributed to it. The IP are in the order： p1〉p2〉p3 but EA are： p1〈p2〈p3. In addition, the decrease of the pyridylene content and the para-linked pyridylene in the backbone of the polythiophene resulted in a narrowed energy gap and bathochromic absorption and emission peaks.     

Synthesis and Structural Characterization of Three Novel Macrocyclic Coordination Complexes Formed by Self-assembly of Bridged Bi-or Tetrapyridine with Transition Metal Salts

Serf-assembly of a ferrocenyl-bridged bipyridine ligand bpef [bpef=1, 1＇-bis（trans-2-pyrid-4＇-ylethenyl）ferrocene] with silver triflate in CH2Cl2/MeOH or mercuric diiodide in MeCN/CH2Cl2 gave the corresponding macrocyclic coordination complexes [bpef]2[AgSO3CF3]2 （1） and [bpef]2[Hg3I6] （2） in 93% and 89% yields, respectively, whereas the pentaerythritolyl-bridged tetrapyridine ligand ptpc [ptpc=pentaerythritol tetrakis-（4-pyridinecarboxylate）] reacted with cobalt thiocyanate via self-assembly to afford the macrocyclic coordination polymer [Co（NCS）2（ptpc）], （3） in 90% yield. The X-ray diffraction analyses for 1-3 confirmed their novel macrocyclic structures and revealed that （i） the two silver atoms in complex 1 have an essentially linear geometry with N-Ag-N bond angle of 175.7° and 172.9°, （ii） the geometry of the middle mercury atom in complex 2 is square-planar, while the other two mercury atoms in the other two complexes are tetrahedral, and （iii） all the cobalt atoms in complex 3 adopt an octahedral geometry. In addition, the synthetic procedure for the known tetrapyridine ligand ptpc has been improved.     

Rapid Thermolysis Studies of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O）

T-jump/FT-IR spectroscopy was used to study the rapid thermal decomposition activity of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O） under 0.1 MPa Ar atmosphere. The results show that the main gaseous products of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O are NH3, H2O and HONO, while CO and NO are the major gaseous products of flash pyrolysis of Cd（CHZ）2（TNR）（H2O）. Thus Cd（CHZ）2（TNR）（H2O） is not an eco-friendly and chemically compatible primary explosive. Both compounds liberate volatile metal carbonate, oxide and isocyanate compounds. The combustion temperature and products of the two compounds were calculated by Real code. The results of theoretical calculation show that the combustion temperature of [Pb2（TNR）2（CHZ）2（H2O）2].4H2O is higher than that of Cd（CHZ）2（TNR）（H2O）, there is no HNCO in the combus- tion products and the amount of NO is less than the experiment result from T-jump/FTIR.