2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶及镍(Ⅱ)配合物的合成与光谱学研究

合成并表征了有机配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶(L)及其镍(Ⅱ)配合物,采用元素分析确定目标配合物组成为C15H21N3O4Ni.H2O,通过对比分析的方法讨论了配位前后游离配体L和镍(Ⅱ)配合物的核磁共振氢谱、核磁共振碳谱、红外吸收光谱和紫外-可见吸收光谱的谱学性质,进而推断出镍(Ⅱ)配合物的结构。结果表明,配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶以2个酰胺负离子N和1个吡啶环N原子为配位原子,与中心金属离子Ni(Ⅱ)通过三齿形式配位;配合物中Ni(Ⅱ)采取dsp2杂化轨道方式与配位原子构成配位键,中心金属Ni(Ⅱ)的配位数为4,1个Ni(Ⅱ)与1个三齿配体L和1个水分子配位,形成平面正方形构型的低自旋镍(Ⅱ)配合物。     

发光性质可调的金属-有机骨架材料[Zn(BDC)(H_2O)_(2-2x)·(8-Hq)_x]的合成及发光性质

以对苯二甲酸(H2BDC)为配体,以锌为中心离子,采用沉淀法合成了具有一维结构的金属配合物[Zn(BDC)(H2O)2]纳米晶,将化合物分散到不同浓度的8-羟基喹啉(8-Hq)溶液中,得到系列配位聚合物[Zn(BDC)(H2O)2-2x·(8-Hq)x]。分别用FT-IR和XRD对目标产物的结构进行了表征。固态发光性质研究显示:[Zn(BDC)(H2O)2]及其配位聚合物具有强的发光,配位聚合物随着8-Hq量的增加,其发光发射光谱有规律地红移,表明该配位聚合物能够通过改变8-Hq与骨架材料间的量的比实现对材料发光性质的调控。     

双核铜配合物[Cu2(pida)2(2,2''-bipy)2]的合成、表征及其结构

N-苯基亚氨基二乙酸,Cu2 离子和2,2'-联吡啶在溶液中组装得到标题配合物[Cu2(Pida)2(2,2'-bipy)2](H2pida=N-苯基亚氨基二乙酸).用元素分析、红外光谱、单晶衍射对配合物的组成和结构进行了表征,结果表明,该标题配合物为N-苯基亚氨基二乙酸根桥联的双核结构,配体pida中的N原子没有参与配位.中心铜离子为五配位畸变的四方锥构型.     

双对二甲氨基苯甲醛缩乙二胺合La(Ⅲ)的合成及抑菌活性

合成了Schiff碱配体双对二甲氨基苯甲醛缩乙二胺(L)及其与La(Ⅲ)形成的新的固体配合物。经元素分析、红外光谱、差热-热重分析、核磁共振氢谱及摩尔电导等表征可知,配合物属于1∶1型的电解质,La(Ⅲ)和来自2个Schiff碱配体的4个N原子以及来自2个硝酸根离子的4个O原子配位,中心La(Ⅲ)离子的配位数为8,配合物可能的结构式为[LaL2(NO3)2]NO3.2H2O。通过琼脂扩散抑菌法测定了产物的抑菌性能,结果表明,该配合物对金黄色葡萄球菌、大肠杆菌和绿脓杆菌具有较好的抗菌活性。     

铜(Ⅱ)配合物与DNA作用的光谱法研究

采用紫外光谱和荧光光谱研究了配离子[Cu(A)₂]2＋(其中A=邻菲络啉(phen),联吡啶(bpy),乙二胺(en))与小牛胸腺DNA的相互作用。实验发现配合物的存在使DNA碱变性的pH增大,变性后增色效应减小。EB-DNA体系的荧光强度随[Cu(phen)₂]2＋的加入迅速减弱。在DNA存在下,配离子被猝灭剂[Fe(CN)₆]4-的发光猝灭程度减小。进一步研究了配体分子平面的大小对配合物与DNA作用的影响。结果表明,铜配合物与DNA之间发生了插入作用,且该作用随配体芳环平面的减小而减弱, 即[Cu(phen)₂]2＋＞[Cu(bpy)₂]2＋＞[Cu(en)₂]2＋。     

新型Schiff碱及其铈(Ⅲ)配合物的合成与表征

在无水乙醇溶剂中,合成双对二甲氨基苯甲醛缩邻苯二胺(L)新型Schiff碱配体,并且在丙酮溶液中合成了它的Ce()配合物。经元素分析、摩尔电导、IR、UV、TG-DTA、1HNMR等分析表明:配合物的可能组成是[CeL2(NO3)2](NO3).2H2O,为1:2(Ce:L)型、含两个结晶水的紫红色固体配合物,电解质类型为1:1型,即配合物外界有1个NO3-,另2个NO3-在配合物的内界以螯合双齿形式参与了配位,中心Ce(Ⅲ)离子的配位数为8。     

铜(Ⅱ)-天冬氨酸-咪唑类配合物的合成及其与DNA作用的光谱研究与比较

合成了两种新的铜(Ⅱ)-天冬氨酸-咪唑类混配配合物([Cu(HAsp)ImH2O]SO4·4H2O与[Cu(Asp)Im (OH)]·4H2O,HAsp代表天冬氨酸分子,Asp代表天冬氨酸离子,Im代表咪唑)。以元素分析、红外光谱及热重-差热分析对其进行表征;以电子吸收光谱法及荧光分析法研究了这两种配合物与DNA的作用。结果表明：两种铜(Ⅱ)-天冬氨酸-咪唑类混配配合物与DNA的作用方式明显不同：[Cu(HAsp)ImH2O]SO4·4H2O为伴随着静电作用的插入结合;而[Cu(Asp)Im (OH)]·4H2O主要与DNA的碱基N发生配位作用,造成了DNA双螺旋的破坏。分析了两种配合物因结构不同而导致的与DNA作用方式不同的原因。     

配合物Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2的合成、光谱表征及荧光性质

以去离子水为溶剂,合成了以Zn2+及N12+为中心,以L1,L2[L1=4-氨基-3,5-二甲基-1,2,4-三唑,L2=4-氨基-1,2,4-三唑]及硫氰酸根为配体的两种配合物,对其进行了元素分析、金属离子络合滴定、摩尔电导测定,确定了配合物组成分别为Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2,同时对两种配合物做了红外光谱、紫外光谱及荧光光谱的测试表征.荧光光谱的测试表明两种配合物均在415 nm有一强的荧光发射峰,且镍配合物的荧光要明显强于锌配合物,两种配合物有望成为蓝光发光材料.     

配合物型分子导体（PyH）［Ni（dmit）2］2的能带结构及其导电性

采用EHMO紧束缚方法计算了配合物型分子导体 (PyH) [Ni(dmit) 2 ] 2 二维阴离子导电层中相邻两 [Ni(dmit) 2 ] - 0 .5 的HOMO轨道的重叠积分 ,并进行了二维能带计算 .计算结果与其单晶变温电导率测试结果一致 ,表明该配合物型分子导体为窄能隙半导体 .在能带计算基础上讨论了该类分子导体导电性与结构的关系 .分子导体的晶体结构对其能带结构和导电性能影响极大 ,分子柱的均匀化 (包括沿分子轴方向的错动尽可能小和面间距均一 )以及小的导电组元分子面间距是有利于增加分子导体的导电性的结构因素     

噻吩甲酰基吡唑啉酮缩β-丙氨酸配合物的合成、表征及极谱行为

在非水溶剂中 ,β 丙氨酸与 1 苯基 3 甲基 4 (2 噻吩甲酰基 )吡唑啉酮 5反应合成新型酰基吡唑啉酮席夫碱化合物 1 苯基 3 甲基 4 (2 噻吩甲酰基 )吡唑啉酮 5缩 β 丙氨酸 (HL) .通过回流席夫碱和金属硝酸盐合成了UO2 (Ⅱ )、Cu(Ⅱ )、Co(Ⅱ )和Fe(Ⅱ )金属配合物 .在乙酸 乙酸钠 (pH =4 .6 )缓冲溶液 饱和甘汞电极体系中 ,测量电位 - 1.2 4V处 ,测得铜配合物的极谱波 .元素分析及摩尔电导值表明 ,新配合物的组成为 [UO2 L2 ]·H2 O ,[CuL2 ]·2H2 O ,[CoL2 ]·2H2 O和 [FeL2 ]·2H2 O .运用红外光谱、紫外光谱、核磁共振谱、热谱和磁矩对配合物进行了表征 .结果表明 ,配合物的中心离子 (除UO2 2 + 以外 )均为 6配位 .铜配合物的Cu2 + 还原产生峰电流 ,其电极反应转移 1个电子 .     

Theoretical Study of the Collision-Induced Double Transition CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) at 296 K

A procedure is presented for the calculation of the double vibrational collision-induced absorption CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) on the basis of quantum lineshapes computed using an isotropic potential and dipole-induced dipole functions. The linestrengths and energies of the vibration-rotation transitions are treated explicitly for N(2), utilizing the HITRAN database for CO(2). The theoretical absorption profile is compared to recent experimental results. By narrowing the width of the individual lines contributing to the overall absorption profile relative to their values determined for N(2)-N(2) collision-induced absorption, excellent agreement between theory and experiment is obtained. Copyright 2000 Academic Press.     

First Observation of the nu(17)-nu(4) Difference Bands of Diborane (10)B(2)H(6) and (11)B(2)H(6)

An analysis of the nu(17)-nu(4) difference bands near 800 cm(-1) of two isotopic species, (10)B(2)H(6) and (11)B(2)H(6), of diborane has been carried out using infrared spectra recorded with a resolution of ca. 0.003 cm(-1). In addition, the nu(17) band of (10)B(2)H(6) has been recorded and assigned. Since this band in (11)B(2)H(6) had already been studied (R. L. Sams, T. A. Blake, S. W. Sharpe, J.-M. Flaud, and W. J. Lafferty, J. Mol. Spectrosc. 191, 331-342 (1998)), it was possible to derive precise energy levels and Hamiltonian constants for the 4(1) vibrational states of both isotopic species. Copyright 2000 Academic Press.     

The Perturbation between the G(1)Pi(g) and 2(1)Delta(g) States of (7)Li(2)

We have observed the rotational levels in the v = 2, 3, 5, 6, 7, and 8 vibrational manifolds of the 2(1)Delta(g) state of (7)Li(2) via the A(1)Sigma(+)(u) intermediate levels by DeltaLambda = 2 transitions. This violation of the DeltaLambda = 0, +/-1 selection rule is due to the interaction with the G(1)Pi(g) state. Band-by-band deperturbations of the G(1)Pi(g) approximately 2(1)Delta(g) (v(Pi), v(Delta)) = (11, 2), (12, 3), (15, 5), (16, 6), (18, 7), and (19, 8) bands have been performed. Deperturbed molecular constants and rotational-electronic interaction parameters are reported here. Copyright 2000 Academic Press.     

Rovibrational Intensities of the (00(0)3) <-- (10(0)0) Dyad Absorption Bands of (12)C(16)O(2)

Absolute line intensities of (12)C(16)O(2) are experimentally measured for the first time for the (00(0)3)(I) <-- (10(0)0)(II) band at 5687.17 cm(-1) and the (00(0)3)(I) <-- (10(0)0)(I) band at 5584.39 cm(-1). The spectra were obtained using a Bomem DA8 Fourier transform spectrometer and a 25-m base-path White cell at NASA-Ames Research Center. The rotationless bandstrengths at a temperature of 296 K and the Herman-Wallis parameters are S(0)(vib) = 6.68(30) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 1.4(9) x 10(-4), and A(2) = -1.1(5) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(II) band and S(0)(vib) = 6.07(22) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 5.2(1.5) x 10(-4) and A(2) = -4.0(7) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(I) band.     

The 2(3)Delta(g) State of (7)Li(2)

Using pulsed perturbation-facilitated optical-optical double resonance (PFOODR) spectroscopy, the 2(3)Delta(g) state of (7)Li(2) (electronic configuration (varsigma(g)2s) (4ddelta(g)), effective principal quantum number n* = 4.101) has been observed and assigned. Molecular constants and a RKR potential energy curve were obtained. The major molecular constants are Copyright 2000 Academic Press.     

CO2同位素分子16O12C16O, 16O12C17O, 16O13C17O配分函数研究

本文主要研究了CO2的三种同位素分子16O12C16O , 16O12C17O ,16O13C17O 70 K~6000 K的总内配分函数 (TIPS)。在总内配分函数的计算中, 转动配分函数的计算采用了McDowell的解析式法, 振动配分函数则采用了简谐振动近似(HOA)获得。最后通过将两配分函数乘积近似计算得出TIPS, 并将其70~3000 K的数据和HITRAN04数据进行了比较, 发现所得结果和数据库符合的较好, 且其误差可以近似看成一条直线。并通过对误差的拟合修订了高温区(3000~6000 K)的计算数据, 给出了在高温下的较为准确的TIPS值。     

The v(1)+v(3) Bands of the (16)O(17)O(16)O and (16)O(16)O(17)O Isotopomers of Ozone

Using 0.002 cm(-1) resolution Fourier transform absorption spectra of an (17)O enriched ozone sample, an extensive analysis of the v(1)+v(3) bands of the (16)O(17)O(16)O and (16)O(16)O(17)O isotopomers of ozone has been performed for the first time. The experimental rotational levels of the (101) vibrational states were satisfactorily reproduced using a Hamiltonian matrix that takes into account the observed rovibrational resonances. More precisely, for (16)O(17)O(16)O, as for the other C(2v)-type ozone isotopomers, it was necessary to account for the Coriolis type resonances linking the (101) rotational levels with the levels of the (200) and (002) vibrational states and the Darling-Dennison interaction coupling the levels of (200) with those of (002). For the C(s)-type isotopomer, namely (16)O(16)O(17)O, as for (16)O(16)O(18)O and (16)O(18)O(18)O, it proved necessary to also account for an additional DeltaK(a)&equals+/-2 resonance involving the rotational levels from (101) and (002) (J.-M. Flaud and R. Bacis, Spectrochimica Acta Part A 54, 3-16 (1998)). Using a Hamiltonian matrix which takes these resonances explicitly into account, precise vibrational energies and rotational and coupling constants were deduced, leading to the following band centers: v(0)(v(1)+v(3))=2078.3496 cm(-1) for (16)O(17)O(16)O and v(0)(v(1)+v(3))=2098.8631 cm(-1) for (16)O(16)O(17)O. Copyright 2001 Academic Press.     

Magnetoelectric effects in multiferroic Y-type hexaferrites Ba_(0.3)Sr_(1.7)Co_xMg_(2-x)Fe_(12)O_(22)

Y-type hexaferrites with tunable conical magnetic structures are promising single-phase multiferroics that exhibit large magnetoelectric effects. We have investigated the influence of Co substitution on the magnetoelectric properties in the Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)(x = 0.0, 0.4, 1.0, 1.6). The spin-induced electric polarization can be reversed by applying a low magnetic field for all the samples. The magnetoelectric phase diagrams of BaBa(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22) are obtained based on the measurements of magnetic field dependence of dielectric constant at selected temperatures. It is found that the substitution of Co ions can preserve the ferroelectric phase up to a higher temperature, and thus is beneficial for achieving single-phase multiferroics at room temperature.