Zur Kenntnis des m,m′-Divinylazobenzols und des m,m′-Divinylazoxybenzols

Ohne Zusammenfassung     

SOLUBLE POLY-(o, m)-TOLUIDINE

The soluble poly-o-toluidine (POT) and poly-m-toluidine (PMT) have been success-fully prepared under controlled conditions of polymerization and post-treatment, andcharacterized by IR, VPO and elemental analysis. It is found that the soluble and insol-uble polymers obtained with two different methods (Ⅰ and Ⅱ) have the similar conduc-tivity and molecular chain structure. VPO measurement shows that the number averagemolecular weight (Mn) of soluble polymers is about 3000. The mole ratio of benzoidto quinoid is about 3:1 according to ~1H-NMR and elemental analysis. Free-standingfilms of intrinsic POT and PMT have been obtained by casting their CHCl_3, THF orDMF solutions onto a glass surface.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Novel Complex [Zn（OHCT）（1,2-BDC）]_n

A novel ligand 11-oxa-4,5,9,10,12,13-hexaaza-cyclopenta [b] triphenylene (OHCT) and its coordination polymer [Zn(OHCT)(1,2-BDC)]n 1 (1,2-BDC = 1,2-benzenedicarboxylate) were synthesized and characterized. Crystallographic data for OHCT: C14H6N6O5, Mr = 274.25, monoclinic, space group P21/c, a = 10.755(3), b = 11.710(4), c = 9.516(3) , β = 108.457(4)o, V = 1136.9(6) 3, Dc = 1.602 g/cm3, μ(MoKα) = 0.111 mm-1, F(000) = 560, Z = 4, the final R = 0.1534 and wR = 0.39709. Crystallographic data for 1: C22H10ZnN6O5, Mr = 503.73, triclinic, space group P , a = 6.1411(5), b = 10.9111(9), c = 14.1925(1) , α = 89.1830(1), β = 79.3030(1), γ = 84.6350(1)o, V = 930.36(1) 3, Dc = 1.798 g/cm3, μ(MoKα) = 1.376 mm-1, F(000) = 508, Z = 2, the final R = 0.0323 and wR = 0.0789. 1 has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different 1,2-BDC ligands and two nitrogen atoms from one OHCT ligand, showing a distorted trigonal bipyramidal configuration.     

Theoretical Studies of the Electronic Structures and Spectrum Properties of Pt n Ni m (n + m = 7, n, m ≠ 0) Clusters

We studied Pt _n Ni _m (n + m = 7, n, m ≠ 0) clusters within the framework of the density functional theory (B3LYP) at the LANL2DZ level. The calculated results show that the Fermi levels are determined by the number of Pt atoms, which gain electrons from Ni atoms. Meanwhile, multifarious orbital hybridization is found in the frontier molecular orbital, and the more platinum or nickel atoms, the smaller energy gap it has. Moreover, the calculated IR and Raman spectrum indicates the aromatic character, which is vital for transitional metal clusters.     

Pt_nNi_m（n＋m=7,n,m≠0）团簇结构稳定性与磁学性质

采用密度泛函理论（DFT）中的杂化密度泛函B3LYP方法在LANL2DZ基组水平上对PtnNim团簇的各种可能构型进行了几何结构全优化,得出了它们的基态构型,并对其稳定性和磁学性质进行了计算研究.研究结果表明：PtnNim团簇的基态结构都为立体结构,对称性较低,多重度较高,Pt5Ni2团簇的稳定性最好;从磁性上看,Pt...     

[Ni（Dpq）（1,3-BDC）]·6H2O的水热合成,晶体结构及电化学行为

以间苯二甲酸（1,3-H2BDC）和二吡啶（3,2-d：2,3′-f）-二氮萘（Dpq）为混合配体,利用水热法合成了一种新的过渡金属配合物[Ni（Dpq）（1,3-BDC）].6H2O,并通过X射线单晶衍射法对其结构进行了测定.结果表明,该化合物属单斜晶系,P2（1）/c空间群,晶胞参数为：a=0.715 98（9）nm,b=1.606 0（2）nm,c=2.410 6（3）nm,Mr=612.15,β=98.482（2）°,V=2.741 5（6）nm3,Z=4,Dc=1.551 g.cm-3,F（000）=1 268.0,μ=0.779 mm-1,R1=0.049,wR2=0.129 9.配合物中镍离子通过Dpq的两个螯合氮原子、1,3-BDC的一个羧基氧原子和三个配位水的氧原子配位,形成六配位的扭曲八面体结构.配合物结构单元间通过氢键和π-π堆积作用形成2D超分子网络结构,并对该配合物的电化学行为进行了研究.     

Triplet states of zigzag edged hexagonal graphene molecules C(6m∗∗2)H(6m) (m = 1, 2, 3, ..., 10) and carbon based magnetism

The geometry and magnetization (spin distribution) of the series of flat hexagonal zigzag edged molecules C(6m??2)H(6m) (m = 1,2, ..., 10) in their lowest triplet state (S(z) = 1) has been calculated using density functional theory and a connection established from the known benzene (m = 1) triplets to the triplets and singlet ground state of the largest molecules (m = 9, 10). The triplet state potential energy surface has two minima corresponding to distortions from the ground state geometry, such that CC bonds bisected by a C(2)" rotation axis are either longer or shorter. For both geometries, the spin on the carbon atoms forms a pattern that peaks at the middle of an edge and for large index (m) values is the same (apart from sign) as the edge pattern of the hexagonally sectored singlet radical ground state of the largest member C(600)H(60). This similarity suggests that the singlet ground state of the larger (m = 9, 10) zigzag edged hexangulenes is possibly a hex-radical, in some ways analogous to the di- and higher multiradical ground state of the linear acenes C(4m + 2)H(2m + 4) starting around m ≥ 8 and 9. The spin patterns provide guidance in interpreting the multiradical nature of ground and low lying excited states of large hexangulenes and how magnetism evolves with size in molecules with graphene cores.     

可溶性聚(o—,m—)甲苯胺

本文通过控制聚合和后处理条件,首次合成了可溶性聚(o-,m-)甲苯胺,用IR,NMR,VPO和元素分析等手段表征了可溶聚合物。结果表明,按两种方法制备的可溶与不溶聚合物具有相同的电导率和链结构。可溶聚合物主链中含有约28个单体单元,苯式(B)与醌式(Q)的比例约为3:1。并由可溶聚合物制备了自支撑膜,掺杂了的自支撑膜具有与粉末同样的电导率和环境稳定性。     

Photoelectron spectroscopy of silicon and germanium-fluorine binary cluster anions (SinF m − , GenF m − )

Electronic properties of silicon-fluorine and germanium-fluorine cluster anions (Si_nF _m ^? n = 1–9, m = 1–3, Ge_nF _m ^? ; n =1–9, m = 1–3) were investigated by photoelectron spectroscopy using a magnetic-bottle type electron spectrometer. The binary cluster anions were generated by a laser vaporization of a silicon/germanium rod in an He carrier gas mixed with a small amount of SiF₄ or F₂ gas. Comparison between photoelectron spectra of Si_nF^?/Ge_nF^? and Sin /Gen (n = 4–9) gives the insight that the doped F atom can remove one electron from the corresponding Sin _n ^? /Ge _n ^? cluster without any serious rearrangement of Sin/Gen framework, because only the first peak of Si _n ^? /Ge _n ^? , corresponding singly occupied molecular orbital (SOMO), disappears and other successive spectral features are unchanged with the F atom doping     

Structural, electronic, bonding, magnetic, and optical properties of bimetallic [Ru(n)Au(m)](0/+) (n + m ≤ 3) clusters

The structural, electronic, bonding, magnetic, and optical properties of bimetallic [Ru(n)Au(m)](0/+) (n + m ≤ 3; n, m = 0-3) clusters were computed in the framework of the density functional theory (DFT) and time-dependent DFT (TD-DFT) using the full-range PBE0 non local hybrid GGA functional combined with the Def2-QZVPP basis sets. Several low-lying states have been investigated and the stability of the ground state spinomers was estimated with respect to all possible fragmentation schemes. Molecular orbital and population analysis schemes along with computed electronic parameters illustrated the details of the bonding mechanisms in the [Ru(n)Au(m)](0/+) clusters. The TD-DFT computed UV-visible absorption spectra of the bimetallic clusters have been fully analyzed and compared to those of pure gold and ruthenium clusters. Assignments of all principal electronic transitions are given and interpreted in terms of contribution from specific molecular orbital excitations.     

[Ni（Dpq）（1,3-BDC）]·6H2O的水热合成,晶体结构及电化学行为

以间苯二甲酸（1,3-H2BDC）和二吡啶（3,2-d：2,3′-f）-二氮萘（Dpq）为混合配体,利用水热法合成了一种新的过渡金属配合物[Ni（Dpq）（1,3-BDC）].6H2O,并通过X射线单晶衍射法对其结构进行了测定.结果表明,该化合物属单斜晶系,P2（1）/c空间群,晶胞参数为：a=0.715 98（9）nm,b=1.606 0（2）nm,c=2.410 6（3）nm,Mr=612.15,β=98.482（2）°,V=2.741 5（6）nm3,Z=4,Dc=1.551 g.cm-3,F（000）=1 268.0,μ=0.779 mm-1,R1=0.049,wR2=0.129 9.配合物中镍离子通过Dpq的两个螯合氮原子、1,3-BDC的一个羧基氧原子和三个配位水的氧原子配位,形成六配位的扭曲八面体结构.配合物结构单元间通过氢键和π-π堆积作用形成2D超分子网络结构,并对该配合物的电化学行为进行了研究.     

在小硅化物SiX^m4（X=H,He,Li,Be,O,F,Ne,Na,Mg,S,Cl,Ar;m=0,…

用从头算方法，在ＨＦ／ＳＴＯ－３Ｇ、ＨＦ／３－２１Ｇ和ＨＦ／６－３１Ｇ水平上研究了小硅化物ＳｉＸ＾ｍ４的成键倾向性。计算结果表明，所研究的分子势能曲线均有稳定的极小值（ＳｉＬｉ４除外）。与已知的稳定分子ＳｉＨ１、ＳｉＦ４和ＳｉＣｌ４比较，含惰性元素的未知分子ＳｉＨｅ＾４＋４、ＳｉＮｅ＾４＋４和ＳｉＡｒ＾４＋４比含碱金属和碱土金属的未知分子ＳｉＬＩ４、ＳｉＮａ４、ＳｉＢｅ＾４＋４和ＳｉＭｇ＾４＋４有     

Die Bedingungen, unter denen eine polarographische Bestimmung von Nitrocyclohexan, einem Zwischenprodukt der Caprolactam-Produktion, m?glich ist

Ohne Zusammenfassung     

Synthesis of leptosin,a glycoside isolated from mānuka honey

The first synthesis of leptosin, a novel glycoside isolated from mānuka honey is described. Utilising an acetyl protecting group strategy the glycoside was obtained with excellent anomeric selectivity by deploying a Schmidt glycosylation as a key step.     

Isomeric yield ratios for the natNd(γ, xn) 139m,g; 141m,gNd reactions in the bremsstrahlung energy region from 45 to 60 MeV

The independent isomeric yield ratios (IR) for the ^139m,gNd and the ^141m,gNd isomeric pairs produced from the ^natNd(γ, xn) reactions were determined by the activation and the off-line γ-ray spectrometric technique at the end-point bremsstrahlung energies of 45, 50, 55, and 60 MeV in the 100 MeV electron Linac of the Pohang accelerator laboratory, Korea. The present IR for the ^141m,gNd isomeric pair were compared with those from the literature measured by the bremsstrahlung and the neutron to examine the role of excitation energy. The obtained IR for the ^139m,gNd and the ^141m,gNd isomeric pairs from ^natNd(γ, xn) reactions were compared with those from the ¹⁴¹Pr(p, x), the ^natCe(³He, x), and the ¹³⁶Ce(α, n) reactions to examine the role of parameters in entrance channel i.e. excitation energy and the effect of the input angular momentum. The present IR of ^139m,gNd and ^141m,gNd were compared with those calculated by using the TALYS 1.4 code as well as those from the literature data of above mentioned reactions.     

High-Tc superconductors studied by57Co,57Fe,119Sn,and151Eu mössbauer spectroscopy

¹⁵¹Eu,¹¹⁹Sn,⁵⁷Fe, and⁵⁷Co Mössbauer spectroscopy was used to study YBa₂Cu₃O_7– high-T_c superconductors in which sites were replaced by various Mössbauer nuclides in order to get information about site preference and structural changes. By decomposition of the Mössbauer spectra, the Y site substituted by Eu and the Cu sites occupied by Sn, Fe, and Co substituents were identified. It was found that Fe and Co prefer the Cu(1) site while Sn prefers the Cu(2) site in the orthorhombic perovskite lattice of these superconductors. The site preference is enhanced in the presence of additional substituents. A sequence of thermal heat treatments permits reversible cycling of⁵⁷Co between the two copper sites in the YBa₂[Cu(⁵⁷Co)]₃O_7– perovskite. In all cases Eu(III) and Sn(IV) states are determined, but the valence state of Fe and Co can be both three and four. BelowT _c, low-temperature phase transformation and phonon softening were shown from the anomalous temperature dependence of isomer shifts and the area fractions of¹⁵¹Eu and¹¹⁹Sn Mössbauer spectra of EuBa₂(Cu_1-xSn_x)₃O_7- cuprates.     

金属串配合物(n,m)[Cr3(PhPyF)4Cl2](n=2, 3, 4; m=2, 1, 0)的配位结构及其与电场的关系

应用密度泛函理论BP86 方法研究具有分子导线潜在应用的金属串配合物(n, m)[Cr₃(PhPyF)₄Cl₂](HPhPyF=N, N'-苯基吡啶基甲脒; n=2, 3, 4; m=2, 1, 0)的配位结构及其受电场作用的影响, n、m分别表示PhPyF-的苯环在左侧和在右侧的配体个数. 结果表明: (1) 零电场下, 四个PhPyF-的(2, 2)、(3, 1)和(4, 0)三种配位方式能量差别很小, 为竞争态, (2, 2)最稳定. (4, 0)结构中两端轴向配体Cl 均可与Cr 配位, 且Cl₄―Cr1 键比Cl5―Cr3键更强, 若作为分子器件可与电极结合, 这与(4, 0)[CuCuM(npa)₄Cl][PF₆](M=Pd, Pt; Hnpa=2-萘啶苯胺)靠近苯环一端的轴向配体无法与M配位不同. (2) 在(2, 2)、(3, 1)和(4, 0)中, Cr₃⁶⁺链均具有三中心三电子离域σ键, 但离域性逐渐减弱. 随四个PhPyF-配位方式趋于一致, 分子极性逐渐增大, 由Cl₄指向Cl5(Z)方向, Cr1的α自旋密度增大, Cr2 的β和Cr3 的α自旋密度减小. (3) 分子的几何结构和电子结构在电场下发生规律性变化, 在-Z方向电场作用下, (3, 1)、(4, 0)电子移动方向与极性方向相同, 使分子的键长、自旋密度、电荷和能隙变化显著性均大于Z方向电场, 且极性越大变化越显著, 有利于提高分子导电性.     

Structure of carbon fluorochlorides CF n Cl m (n,m ≤ 3) and their singly charged negative ions

The electronic and geometrical structures of carbon fluorochlorides with low coordination numbers (n 3) and their singly charged anions are calculated using the functional density method. The results of the calculations are used to evaluate the electron affinities (EA) of the neutral compounds and the first ionization potentials of the anions as well as the energies of fragmentation through different decay channels of both series. The adiabatic EA of carbon fluorochloride CF _k Cl _3–k is shown to be determined mainly by the presence of a CX₂ unit in these compounds. There are no monotonic changes in stability of either the neutral compounds withn = 3 or the anions withn = 2 or 3 upon successive substitution of one halogen by another.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1044–1049, June, 1993.