过渡金属吡啶配离子的TCNQ电荷转移盐的合成和物理性质

合成了通式为[M(Py)_m][TCNQ]_n(M=Mn,m＝4;M＝Co,Ni,Cu,m＝2;TCNQ＝7,7,8,8-四氰基对苯醌二甲烷,n＝2,3)的8个过渡金属吡啶配离子的TCNQ电荷转移盐,通过元素分析、红外光谱、顺磁共振谱、光电子能谱、磁化率和电导率对这些电荷转移盐进行了表征,结果表明,在这些电荷转移盐分子中存在TCNQ^-和TCNQ⁰,且TCNQ^-与TCNQ⁰相互作用形成结构单元[TCNQ]_n^2-(n＝2,3),各个结构单元沿一维方向堆积形成分子柱,部分电荷从[TCNQ]_n^2-向[M(Py)_m]²⁺转移,导致化合物中的金属表现为混合价态.其中3个电荷转移盐具有良好的导电性.     

双（1,2—丙二胺）合铜的TCNQ盐的合成与光谱研究

合成了导电性ＴＣＮＱ盐Ｃｕ（ｐｎ）２（ＴＣＮＱ）ｎ（ｎ＝２和３，ｐｎ＝１，２－丙二胺，ＴＣＮＱ＝７，７，８，８－四氰基对苯二醌二甲烷）。红外光谱、电子光谱和Ｘ－光电子能谱研究表明ＴＣＮＱ盐中存在ＴＣＮＱ°和ＴＣＮＱ－，ＴＣＮＱ°与ＴＣＮＱ－之间发生了部分电子转移，致使铜呈混合价态。它们的粉末室温电导率为１．１×１０－５～２．４×１０－６ｏｈｍ－１ｃｍ－１。     

4,4'-联吡啶、吡嗪和咪唑桥联铜、镍配合物的合成和磁性

合成了六个含氮杂环桥联配合物: [Ni(salal)2(4,4'-bipy)]n、[Ni(Et-dtp)2(4,4'-bipy)]n、[Cu(acac)2(4,4'-bipy)]n、[Cu(TTA)2(pyz)]n、[Cu(TTa)(Im)]n和[Cu(Im)2]n, 用元素分析、IR、MS、ESR和热重分析对它们的结构和性质作了表征。吡嗪配合物的晶体结构显示, 吡嗪配位于拉伸八面体的轴向位置, 桥联Cu(TTA)2形成一维无限链状结构。变温磁化率表明, 4,4'-联吡啶和吡嗪配合物的磁性遵从Curie-Weiss定律, 分子内没有明显的磁交换作用。咪唑配合物中存在着较强的反铁磁性交换作用, 磁交换常数分别为-75和-107cm^-^1。对4,4'-联吡啶、吡嗪和咪唑传递磁交换的性质作了讨论。     

铜(II)与α, β-不饱和酸根形成的超分子配合物的合成、磁性 及晶体结构

合成了铜(II)与丙烯酸根和铜(II)与α-甲基丙烯酸根形成的两种超分子配合物,进行了元素分析、红外光谱、ESR谱和磁性等研究,确定分子单元的组成为Cu~2A~4(H~2O)~2,其中A=CH~2=CH-COO^-,CH~2=C(CH~3)-COO^-。测定了铜(II)与丙烯酸根形成的配合物的晶体结构。晶体属单斜晶系;C2/c群;晶胞参数:a=1.7009(9)nm,b=0.8060(5)nm,c=1.4429(4)n,β=109.31(5)ⅲ,Z=4;最终偏离因子R=0.0501。Cu(II)具有畸变的四角锥形配位环境,两个Cu(II)由四个丙烯酸根桥联,在Cu(II)的端位各有一个H~2O分子配位。Cu(II)-Cu(II)间具有一对称中心,Cu-Cu间距离为0.26096(14)nm,两个Cu(II)间具有反铁磁性偶合作用。每个分子单元以四根氢键与相邻的两个分子单元相连接,沿c轴形成一维链状超分子配合物。     

铜(II)与α, β-不饱和酸根形成的超分子配合物的合成、磁性 及晶体结构

合成了铜(II)与丙烯酸根和铜(II)与α-甲基丙烯酸根形成的两种超分子配合物,进行了元素分析、红外光谱、ESR谱和磁性等研究,确定分子单元的组成为Cu~2A~4(H~2O)~2,其中A=CH~2=CH-COO^-,CH~2=C(CH~3)-COO^-。测定了铜(II)与丙烯酸根形成的配合物的晶体结构。晶体属单斜晶系;C2/c群;晶胞参数:a=1.7009(9)nm,b=0.8060(5)nm,c=1.4429(4)n,β=109.31(5)ⅲ,Z=4;最终偏离因子R=0.0501。Cu(II)具有畸变的四角锥形配位环境,两个Cu(II)由四个丙烯酸根桥联,在Cu(II)的端位各有一个H~2O分子配位。Cu(II)-Cu(II)间具有一对称中心,Cu-Cu间距离为0.26096(14)nm,两个Cu(II)间具有反铁磁性偶合作用。每个分子单元以四根氢键与相邻的两个分子单元相连接,沿c轴形成一维链状超分子配合物。     

铜(Ⅱ)与反式丁烯二酸根和2,2'-联吡啶配合物的研究

合成了铜(Ⅱ)与反式丁烯二酸根和2,2'-联吡啶形成的配合物,并进行了元素分析、红外光谱、电子反射光谱和变温磁化率等研究,确定其组成为[Cu~2(fum)(bipy)~4][fum]·12H~2O,其中bipy=2,2'-联吡啶,fum=反式丁烯二酸根。测定了配合物的晶体结构,[Cu~2(fum)(bipy)~4][fum]·12H~2O晶体属三斜晶系,P1(#2)群;晶胞参数：a=1.0697(2)nm,b=1.2820(2)nm,c=1.0470(3)nm,α=101.88(2)°,β=101.93(2)°,γ=79.41(1)°;Z=1,最终偏离因子R=0.033。分子为反式丁烯二酸根桥联两个Cu(Ⅱ)单元的双核结构,每个Cu(Ⅱ)具有畸变的三角双锥配位环境。变温磁化率研究表明,配合物中存在弱的铁磁性偶合作用。     

N,N'-乙二水杨酰胺合铜(II)酸根和N,N'-1,2-丙二水杨酰胺全铜(II)酸根的双核Cu(II)-Fe(III)配合物的合成和磁性

本文合成了四个新型双核配合物、[Cu(samen)Fe(L)Cl]和[Cu(sampn)Fe(L)Cl]。经元素分析、IR, 电导、磁性测量等手段推定配合物具有酚氧桥结构, Cu(II)及Fe(III)的配位环境分别为平面四方及四角锥的构型, Fe(III)离子的自旋态S=3/2。测定了配合物[Cu(samen)Fe(L)Cl]的变温磁化率(4-300K), 参数J和θ值表明两个双核配合物中金属离子之间有中等程度的反铁磁性超交换作用和双核单元之间有弱的分子间相互作用。     

铜(Ⅱ)与α,β-不饱和酸根和乙酰胺配合物的合成、表征、晶体结构和磁性

合成了铜(Ⅱ)与丙烯酸根和乙酰胺及铜(Ⅱ)与α-甲基丙烯酸根和乙酰胺两种配合物,进行了元素分析、红外光谱、电子光谱、ESR谱和变温磁化等研究,确定配合物的组成为Cu~2A~4(C~2H~5NO)~2,其中A=CH~2＝CHCOO^-,CH~2＝C(CH~3)COO^-;C~2H~5NO=乙酰胺,测定了它们的晶体结构。Cu~2(CH~2＝CHCOO)~4(C~2H~5NO)~2(1)晶体属单斜晶系,P2~1/c群;晶胞参数：a=1.5333(5)nm,b=1.0044(3)nm,c=1.6184(7)nm,β=115.28(3)°;Z=4;最终偏离因子R=0.0701。Cu~2[CH~2＝C(CH~3)COO]~4(C~2H~5NO)~2(2)晶体属三斜晶系,P1群;晶胞参数：a=0.93327(11)nm,b=1.12484(11)nm,c=1.3740(6)nm,α=94.90(2)°,β=108.409(14)°,γ=110.556(5)°;Z=2;最终偏离因子R=0.0351。配合物中Cu(Ⅱ)具有畸变的四角锥形配位环境,两个Cu(Ⅱ)由四个α,β-不饱和酸根桥联,在Cu(Ⅱ)的端位各有一个乙酰胺分子以O原子配位。Cu(Ⅱ)－Cu(Ⅱ)间具有一对称中心。配合物1中Cu(Ⅱ)－Cu(Ⅱ)间距离为0.26302(13)nm,配合物2中Cu(Ⅱ)－Cu(Ⅱ)间距离为0.26383(4)nm。变温磁化率研究表明,两种配合物中Cu(Ⅱ)－Cu(Ⅱ)间具有强烈的反铁磁性偶合作用。     

铜(Ⅱ)与反式丁烯二酸根和2,2'-联吡啶配合物的研究

合成了铜(Ⅱ)与反式丁烯二酸根和2,2'-联吡啶形成的配合物,并进行了元素分析、红外光谱、电子反射光谱和变温磁化率等研究,确定其组成为[Cu~2(fum)(bipy)~4][fum]·12H~2O,其中bipy=2,2'-联吡啶,fum=反式丁烯二酸根。测定了配合物的晶体结构,[Cu~2(fum)(bipy)~4][fum]·12H~2O晶体属三斜晶系,P1(#2)群;晶胞参数：a=1.0697(2)nm,b=1.2820(2)nm,c=1.0470(3)nm,α=101.88(2)°,β=101.93(2)°,γ=79.41(1)°;Z=1,最终偏离因子R=0.033。分子为反式丁烯二酸根桥联两个Cu(Ⅱ)单元的双核结构,每个Cu(Ⅱ)具有畸变的三角双锥配位环境。变温磁化率研究表明,配合物中存在弱的铁磁性偶合作用。     

四芳基卟啉锰配离子的TCNQ电荷转移盐的合成和物理性质

合成了13个四芳基卟啉锰配离子的TCNQ电荷转移盐[TAPMn][TCNQ]_n(TAPH₂=α,β,γ,δ-四芳基卟啉;A=C₆H₅,4-CH₃C₆H₄,4-CH₃OC₆H₄,4-ClC₆H₄,3-ClC₆H₄,3-FC₆H₄,4-(CH₃)₂NC₆H₄,2,4-Cl₂C₆H₃;TCNQ=7,7,8,8-四氰基对苯醌二甲烷;n=1,2).通过元素分析、IR、XPS、ESR、磁化率和电导率对其进行了表征.结果表明:这些电荷转移盐分子中存在TCNQ⁰和TCNQ^-,且TCNQ⁰和TCNQ^-之间存在相互作用,部分电荷从[TCNQ]_n^-向[TAPMn]⁺转移,导致化合物中的锰表现为混合价态.复合盐的室温电导率在10^-7～10^-10S·cm^-1,属于有机半导体,简单盐的室温电导率小于10^-11S·cm^-1.     

Synthesis and properties of catechol-fused tetrathiafulvalene derivatives and their hydrogen-bonded conductive charge-transfer salts

Catechol-fused tetrathiafulvalene (TTF) derivatives have been designed and synthesized as a new type of π-electron donor molecules having two phenolic hydroxyl groups. Cyclic voltammetry measurements and quantum chemical calculations demonstrated the electronic effect of the direct fusion of the catechol unit to the TTF π-skeleton. In the charge-transfer (CT) salts with bromide or chloride anions, a one-dimensional hydrogen-bonded chain was formed by the intermolecular OH?X network between the catechol moieties and the halide anions. The slight dissimilarity of the hydrogen-bond distances for the two CT salts gave rise to the significant differences in their overall molecular arrangements and intermolecular interactions as well as the electrical resistivities.     

Synthesis,characterization and complexation studies of bis-oxy biphenyl based novel diamides

A series of bis-oxy biphenyl based diamides have been synthesized and characterized from spectral and XRD data. All the diamides form charge-transfer (CT) complex with 7,7,8,8-tetracyanoquinodimethane (TCNQ).     

Structure and growth of oxides on polycrystalline nickel surfaces

The oxidation of polycrystalline nickel (Ni) metal surfaces after exposure to oxygen gas (O₂) at 25 and 300 °C and pressures near 130 Pa, was studied using X‐ray photoelectron spectroscopy (XPS). Oxide structures involving both divalent (Ni²⁺) and trivalent (Ni³⁺) species could be distinguished using Ni 2p spectra, while surface adsorbed O₂ and atomic oxygen (O) species could be differentiated from bulk oxide (O^2?) using O 1s spectra. Oxide thicknesses and distributions were determined using QUASES^?, and the average oxide thickness was verified using the Strohmeier formula. The reaction kinetics for oxide films grown at 300 °C followed a parabolic mechanism, with an oxide thickness of greater than 4 nm having formed after 60 min. Exposure at 25 °C followed a direct logarithmic mechanism with an oxide growth rate about four to five times slower than at 300 °C. Reaction of a Ni (100) single crystal under comparable conditions showed much slower reaction rates compared to polycrystalline specimens. The higher reaction rate of the polycrystalline materials is attributed to grain boundary transport of Ni cations. Oxide thickness was measured on a microscopic scale for polycrystalline Ni exposed to large doses of O₂ at 25 and 300 °C. The thickness of oxide was not strongly localized on this scale. However, the QUASES^? analysis suggests that there is localized growth on a nanometric scale—the result of island formation. Copyright © 2007 John Wiley & Sons, Ltd.     

碲化银纳米晶的室温合成及表征

在室温下制备了碲化银纳米粒子,制备过程中选用了新型的还原剂多聚甲醛。所得产物用X射线光电子能谱、X射线粉末衍射和透射电镜进行了表征。     

Synthesis,structure and physical properties of nickel bis(dithiolene) complexes with different cations

A series of new complexes of multi-sulfur 1,2-dithiolene ligands, [Ru(bipy)₃][Ni(L)₂]₂ (bipy?=?2,2′-bipyridine; L?=?pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate), dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate)), have been synthesized and characterized. One typical complex, [Ru(bipy)₃][Ni(pddt)₂]₂·2H₂O (1), crystallized in an acentric space group of P2₁2₁2₁, with the cell dimensions of a?=?8.634(1), b?=?14.560(1), c?=?49.889(5)?Å, α?=?β?=?γ?=?90°, and Z?=?4. It consists of alternating columns of cations and anions along the a direction. The structure was refined by full matrix least squares methods to R ₁?=?0.0340, wR ₂?=?0.0670. Magnetic studies on [Ph₂Cr][Ni(dddt)₂] are also reported.     

Synthesis,crystal structure and magnetic properties of a nickel(II) complex containing a 2-pyridyl-substituted nitronyl nitroxide

A new complex of formula [Ni(NIT2Py)₂Cl(H₂O)]Cl·2CH₃OH, where NIT2Py is 2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, was synthesized and characterized structurally and magnetically. The structure consists of a [Ni(NIT2Py)₂Cl(H₂O)]⁺ ion, a chloride anion and two methanol molecules. The nickel(II) ion lies in a distorted octahedral environment; two nitrogen atoms and two oxygen atoms from NIT2Py ligands from the basal plane; one oxygen atom from a water molecule and one chloride anion occupy axial positions. Variable temperature magnetic susceptibility data show that there is strong antiferromagnetic coupling between the nickel(II) ion and nitronyl nitroxide radicals. The results suggest that the sign of the magnetic interaction depends on structural and ligand effects.     

XPS and XAES analysis of copper,arsenic and sulfur chemical state in enargites

Enargite, a copper arsenic sulfide with the formula Cu₃AsS₄ is of environmental concern due to its potential to release toxic arsenic species. The oxidation and dissolution of enargite are governed by the composition and chemical state of the outermost surface layer. Qualitative and quantitative analysis of the enargite surface can be initially obtained on the basis of X‐ray photoelectron spectroscopy (XPS) binding energy and intensity data. However, a more precise determination of the chemical state of the principal elements of enargite (copper, arsenic and sulfur) in the altered surface layer and in the bulk of the mineral requires a combined analysis based on XPS photoelectron lines and the corresponding X‐ray excited Auger lines. On the basis of results obtained on natural and synthetic enargite samples and on standards of sulfides and oxides, the Auger parameter α′ of different compounds was calculated and the Wagner chemical state plots were drawn for arsenic, copper and sulfur. Arsenic in enargite is found to be in a chemical environment similar to that of arsenides or elemental arsenic, whereas copper in enargite is in a chemical state that corresponds to copper sulfide, Cu₂S, for all samples irrespective of surface treatment (natural or freshly cleaved). Only sulfur changed from a chemical state similar to that of copper or iron sulfide in freshly cleaved samples to another state in natural enargite in the as‐received state. Thus, it is the sulfur atom at the surface of enargite that is most susceptible to changes in the enargite surface state and composition. A more detailed interpretation of this behavior, based on differences in the initial and final state effects, is proposed here. The concept of Auger parameter and chemical state plot, used here for the first time for investigating enargite, has proved to be a method to unambiguously assign the chemical state of the principal elements copper, arsenic and sulfur in these minerals. Copyright © 2006 John Wiley & Sons, Ltd.