Synthesis and photoconductivity study of phthalocyanine polymers. V. 4,4′-diamino-diphenyl ether bridged polymeric SiPc

A novel polymer with quasi-one-dimensional structure of 4,4′-diamino-diphenyl ether bridged polymeric silicon phthalocyanine ( I ) is synthesized by the condensation polymerization of 4,4′-diamino-diphenyl ether (DDE) monomer and dichloride silicon phthalocyanine (Cl₂SiPc) monomer. The structure of the polymer ( I ) is identified by IR subtraction and UV/VIS spectroscopy and elemental analysis. The photoconductivity of the polymer I with quasi-one-dimensional structure is better than that of not only the parent Cl₂SiPc reactant, but also other polymeric phthalocyanines without one-dimensional structures, and showing one-dimensional effect of molecular structure. © 1997 John Wiley & Sons, Inc.     

Synthesis and photoconductivity study of phthalocyanine polymers. II. PVK-co-CuPc (COOH)3

Cu-phthalocyanine diimide (Cu-diPc) was synthesized from a mixture of phthalic anhydride and pyromellitic dianhydride. By the hydrolysis of Cu-diPc, Cu-4,4′,5,5′-tetracarboxy-phthalocyanine (Cu-taPc) was obtained. A novel polymer of polyvinylcarbazole-bonded CuPc(COOH)₃ ( I ) was synthesized by the Friedel–Crafts reaction of polyvinylcarbazole (PVK) with Cu-phthalocyanine-4,4′,5,5′-tetraacid chloride. Polymer ( I ) contains ca. 5 mol % CuPc(COOH)₃ rings, which are covalently bonded to PVK. Polymer ( I ) shows good photoconductivity, which is much better than that of the corresponding phthalocyanine monomers. The factors that influence the photoconductivity, such as the thickness of IFL, and the types and proportion of CTM, were also studied. © 1993 John Wiley & Sons, Inc.     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Electrical conductivity and photoconductivity of films of composites based on poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] with additions of zinc octabutyl phthalocyanine and C60

Features of the photoconductivity of films of composites based on [2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] with additions of zinc 2,3,9,10,16,17,23,24-octabutylphthalocyanine and C₆₀ were studied. Luminescence quenching and an increase in the photoconductivity with the addition of C₆₀ to their composition were detected. The increase in the photoconductivity is connected with the capture of electrons and their transport along the C₆₀ molecules. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 271–275, September–October, 2006.     

钒磷酸盐(NH3CH2CH2NH2)[VOPO4]的水热合成和结构表征

标题化合物是在反应物摩尔比为V2O5H3PO4H2NCH2CH2NH2H2O=0.5543.6265时,175℃水热反应5 d合成的.其结构特点是钒八面体[VO5N]共用角顶的氧形成"之"字型链,链间由[PO4]共角项连接成层;乙二胺分子的一个N直接与V配位,并伸向层间.相邻层间存在强氢键.晶体学数据单斜晶系,P21/c(No.14),a=0.92108(2)nm,b=0.72851(1)nm,c=0.98204(2)nm,β=101.269(7)°,V=0.6462(4)nm3,Z=4,Dc=2.303g·cm-3,R1=0.0417,wR2=0.0999.     

Synthesis and Crystal Structure of Cadmium（Ⅱ） Complex [Cd（H2O）（CH3OC6H4COO）2]n

1 INTRODUCTION Cadmium (Ⅱ) complexes have been exten- sively studied from both chemical and structural views, mainly due to the capability of cadmium (Ⅱ) (shared by most d10 metal ions) to adopt different modes of coordination determined by the consideration of size, as well as electrostatic and covalent bonding forces[1]. And the field of coordination polymers has witnessed tremendous growth over the last decade[2]. Many coordination polymeric networks have been shown to posses intere…     

[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O的水热合成与表征

首次合成了[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O,通过元素分析、红外光谱和X射线单晶衍射对合成产物进行了表征,并用TGA-DSC研究了化合物的热稳定性.晶体属单斜晶系,P21/m空间群,a=1.2596(3)nm,b=1.8715(4)nm,c=1.9816(4)nm,α=γ=90°,β=90.16(3)°,V=4.671(2)nm3,Z=2,Mr=4358.66,Dc=3.100g·cm-3,μ=19.978mm-1,F(000)=3792,R=0.0835,Rw=0.2026.结果表明,在晶体结构内形成了0.7364nm×0.8354nm的微孔.     

Comparative study of structural stability in [NH4−n (CH3) n ]2HgCl4 and in related compounds

The structural instability of the [NH_4−n (CH₃) _n ]₂HgCl₄ group has been investigated. Consideration of different crystals of this family shows that the H-bonds, obviously, hinder the appearance of incommensurate modulation. The dependence of phase transition sequence on the sizes of cation and anion may be obtained only for crystals with simple cation. The appearance of H-bonds complicates the situation and, leads to gradual disappearance of IC phase in the A₂BX₄ family.     

[In2(HPO3)4]·(NH3CH2CH2NH3)的水热合成与晶体结构

用乙二胺作模板剂在水热条件下合成出一个新的三维开放骨架结构的亚磷酸铟[In2(HPO3)4]·(NH3CH2CH2NH3)(1), 并对其晶体结构进行了测定和表征.     

An ab initio molecular orbital study of the grignard reagents CH3MgCl and [CH3MgCl]2: The Schlenk equilibrium

Ab initio molecular orbital calculations are used to study the modified Schlenk equilibrium: 2RMgCl (RMgCl)² MgR₂ + MgCl₂ Mg(Cl₂)MgR₂ with R=H and CH₃. In the absence of any solvents, calculations indicate that the formation of the various possible bridged dimers (RMgCl)₂ is substantially exothermic. However, using dimethylether as a model solvent, we show that the formation of the dimer (Me₂O)(CH₃)Mg(Cl₂)Mg(CH₃)(OMe₂) is exothermic only when entropic effects are included.     

Die Reaktion des [(Me3Si)2CH]2Al?CH2?Al [CH(SiMe3)2]2 mit Neopentyllithium: Bildung des {[(Me3Si)2CH]2Al?CH2?Al [CH(SiMe3)2]2CH2CMe3}⊖ [Li(TMEDA)2]⊕

Reaction of [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ with Neopentyllithium: Formation of {[(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂CH₂CMe₃} ? [Li(TMEDA)₂]⊕ The recently synthesized methylene bridged dialuminium compound [(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂ reacts with neopentyl lithium in the presence of TMEDA to give the stable {[(Me₃Si)₂CH]₂Al? CH₂? Al [CH(SiMe₃)₂]₂CH₂ · CMe₃}? [Li(TMEDA)₂]⊕ decomposing at 115°C. The aluminium atoms therein are not additionally bridged, but the new substituent is occupying a terminal position as detected by crystal structure determination. A compound is formed containing a saturated, fourfold coordinated neighbouring a formally unsaturated, threefold coordinated aluminium atom. Due to high sterical restrictions the Al? C bonds are lengthened up to 209.0(3) pm at the alanate site and the Al? C? Al angle in the methylene bridge is extraordinarily enlarged to 144.4(2)°.     

Solvothermal Synthesis and Crystal Structure of [H2N（CH2）2NH3]{Co[H2N（CH2）2NH2]3}[SbSe4]

1 INTRODUCTION The chalcogenidometallates with open frame- works have attracted considerable interest as pos- sible zeolite-like materials, of which highly interes- ting properties could be expected. Over the last de- cades a large number of thioanti…     

Synthesis,Crystal Structure,and Spectroscopic Characterization of the Borazine Derivatives [B{CH2(SiCl3)}NH]3 and [B{CH2(SiCl2CH3)}NH]3

The borazine derivatives B, B′, B″‐tris[(trichlorosilyl)methyl]borazine [B{CH₂(SiCl₃)}NH]₃ ( 1 ), and B, B′, B″‐tris[{dichloro(methyl)silyl}methyl]borazine [B{CH₂(SiCl₂CH₃)}NH]₃ ( 2 ) were prepared by reacting (Cl₃Si)CH₂(BCl₂) ( 3 ) and [Cl₂(CH₃)Si]CH₂(BCl₂) ( 4 ) with hexamethyldisilazane (hmds), respectively. Both compounds, 1 and 2 crystallize in space group R3c with a = 1712.53(4), c = 1230.33(4) pm, Z = 6, R₁ = 0.030, and a = 1713.8(2), c = 1258.7(2) pm, Z = 6, R₁ = 0.034, respectively. According to the single crystal X‐ray diffraction analyses, the title compounds show a planar B₃N₃ six‐membered ring with B—N distances of 142.3(3) pm (point symmetry C₃) and synfacial oriented substituents. The borazine derivatives have also been characterized by NMR and IR spectroscopy as well as by MS spectrometry.     

Solution and solid-state study of heteroleptic Hg(II)-thiolates: crystal structures of [Hg4I4(SCH2CH2NH2)4] and [Hg4I8(SCH2CH2NH3)2]n.nH2O

Combination of 2-aminoethanethiol hydrochloride and HgI2 in water in the presence of a base yielded a cyclic molecular structure, [Hg4I4(SCH2CH2NH2)4] (1). For the same reaction in the absence of the base, a similar structure with protonated amines was expected; however, polymeric [Hg4I8(SCH2CH2NH3)2]n.nH2O2 was formed instead. The structures are quite variable despite similar reaction conditions. For instance, there is an additional Hg-N interaction in 1 due to the use of base. The environment around tetracoordinate Hg in 1 is comprised of S, N, and I atoms, with the ligand forming a five-membered chelate and the I atoms present alternate to each other. In the repeating unit of 2, three independent types of Hg atoms are observed, with HgSI3, HgS2I2, and HgI4 bonding environments that have both bridging and terminal I atoms. A simple mechanistic pathway for the formation of 1 and 2 is proposed that includes the presence of three- and four-coordinate Hg intermediates in the solution. Intermolecular hydrogen bonding involving N, I, and S in 1 and N, I, and O atoms in 2 create extended three-dimensional networks. The shortest Hg... Hg distances are found to be intrachain in the range 3.938-3.962 A and indicate no interaction between these atoms. The solution studies (UV-vis and NMR) along with solid-state (IR, Raman, and X-ray) studies for 1 and 2 confirm retention of the structural configuration in the solution. The thermal study of 2 indicates that degradation of the complex occurs in a single step, in contrast to 1, which takes a more complicated decomposition pathway.     

Synthesis, Structure Characterization and Biological Activity of Layered Vanadium Oxides [ NH3 （ CH2 ）2 NH （ CH2 ）2 NH3 ] [ V6 O14 ]

Introduction Over the past decades, polyoxometalates(POMs)have been attracting extensive interestowing to the widerange of their topological properties and potential appli-cations in catalysis, photochemistry, electrochromism,and magnetism[1,2]. Meanwhile, owing to the potentialapplication of polyoxometalaes as anticancer and antivi-ral drugs, their complexes have attracted increasing in-terest of both inorganic chemists and biochemists[3]. Itis well known that polyoxometalates are excellent …     

High-spin carboxylate polymers [M(OOCCMe3)2]n of group VIII 3d metals

A coordination polymer of the general formula [Co(OOCCMe₃)₂]_n (2) was prepared by mild thermolysis of the coordination polymer of variable composition [(HOOCCMe₃)_xCo(OH)_n(OOCCMe₃)_2−n ]_m, the dinuclear cobalt complex Co₂(μ-H₂O)(OOCCMe₃)₄(HOOCCMe₃)₄, the tetranuclear cobalt cluster Co₄(μ₃-OH)₂(OOCCMe₃)₆(HOEt)₆, and the hexanuclear cluster [Co₆(μ₄-O)₂(μ_n-OOCCMe₃)₁₀(C₄H₈O)₃(H₂O)]·1.5(C₄H₈O) (7) in organic solvents. In the crystal, the polymer has a chain structure. Unlike thermolysis of cobalt pivalates, thermolysis of the dinuclear complex Ni₂(μ-H₂O)(OOCCMe₃)₄(HOOCCMe₃)₄ gave rise to the hexanuclear complex Ni₆(μ₂-OOCCMe₃)₆(μ₃-OOCCMe₃)₆ (3). The magnetic properties of compound 2 are substantially different from those of 3. Compound 2 undergoes the magnetic phase transition into the ordered state at T _c = 3.4 K (H = 1 Oe), whereas compound 3 exhibits antiferromagnetic properties. Solid-state decomposition of polymeric cobalt carboxylate 2 (below 350 °C) afforded the octanuclear cluster Co₈(μ₄-O)₂(μ₂-OOCCMe₃)₆(μ₃-OOCCMe₃)₆ (9) as the major product, which sublimes without decomposition. Decomposition of 3 gave nickel oxide as the final product. Pivalates 2 and 3 reacted with 2,3-lutidine in acetonitrile at 80 °C to form the isostructural dinuclear complexes (2,3-Me₂C₅H₃N)₂M₂(μ-OOCCMe₃)₄ (M = Co or Ni). The structures of compounds 3 and 7 were established by X-ray diffraction. The structure of polymer 2 was determined by powder X-ray diffraction analysis. Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1841–1850, November, 2006.     

[(NH2CH2CH2NH3)2WⅥO2(NHC6H4NH)2]2(NH2CH2CH2NH2)·H2O配合物的合成与晶体结构

Cis-dioxo-tungsten(Ⅵ) complex, (NH₂CH₂CH₂NH₂)[(NH₂CH₂CH₂NH₃)₂W^ⅥO₂(NHC₆H₄NH)₂]₂·H₂O is synthesized at room temperature by the reaction of sodium tungstate with o-phenylenediamine. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/ c, a=0.712 8(2) nm, b=3.081 1(10) nm, c=0.981 9(3) nm, β=102.615(4)°, V=2.104 4(11) nm³, Z=2, μ=55.26 cm^-1, F(000)=1 176. Compared the complex with its analogous biomimetic complexes of the cofactor of molybdoenzymes and tungstoenzymses, it is found that the variance of the coordination atoms and the metal ions center have no influence on the coordination feature, and exhibits distored octahedral coordination with cis-dioxo o-phenylenediamine. CCDC: 252834.     

Synthesis of some [n.1.3.1]- and [n.1.2.1] paddlanes

The synthesis of 3 dithiapaddlanes is described.