Kinetics on Thermal Decomposition of Iron(III) Complexes of 1,2-Bis(Imino-4’-Antipyrinyl)Ethane with Varying Counter Anions

A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.

环金属配体Ir(Ⅲ)配合物结构、光谱和量子效率的理论研究

对一类环金属Ir(Ⅲ)[(C^N)_(2)Ir(A^A)]配合物[C^N=ptaz(1,2,4),mhtz(3),ptaz=3,4,5-三苯基-4H-1,2,4-三唑,mhtz=1,3-双甲基-5-苯基-1H-1,2,4-三唑;A^A=pzpy(1),npzpy(2,3),bicb(4),pzpy=2-(1H-吡唑-1-基)吡啶,npzpy=4-二甲基氨基-2-(1H-吡唑-1-基)吡啶,bicb=3,3′-亚甲基双(1-甲基-1H-咪唑-2-亚基)]的结构、光谱特征和磷光量子效率进行了理论研究.计算方法探究表明,基于B3LYP泛函优化的基态结构和单激发组态相互作用(CIS)方法得到的激发态结构计算的吸收和发射光谱更准确.配合物1~4的最低吸收峰和发射峰分别位于408,376,382,365 nm和503,506,468,511 nm处,其HOMOs主要由金属和C^N配体占据,而配合物1~3的LUMOs由A^A配体的π反键轨道组成,配合物4的LUMO存在于C^N配体上.因此,配合物4的最低吸收峰和发射峰具有与配合物1~3不同的金属到配体和配体内部(MLCT/ILCT)的混合跃迁性质,非共轭N^N配体的引入显著消弱了其在跃迁过程中的贡献程度.配合物1~4的量子效率取决于非辐射跃迁速率常数k_(nr),这与它们重组能的贡献[4569 cm^(-1)(3)>2583 cm^(-1)(1)>1232 cm^(-1)(2)>975 cm^(-1)(4)]相一致,表明主配体的体积和辅助配体的共轭能力都能影响配合物的磷光量子效率.

Syntheses, Crystal Structures and IR Spectra of Two Mixed Metal Complexes:〔Cr_nFe_(3-n)(μ_3-O)-(μ-O_2CC_2H_5)_6 Py_3〕Cl(n=1,2)

Two mixed metal complexes [Cr2Fe(μ3-O) (μ-O2CC2H5)6Py3]Cl (A)and [CrFe2 (μ3-O) (μ-O2CC2H5 )6Py3] Cl (B) have been prepared in non-aqueous sol-vents. Crystal (A) is monoclinic, space group C2/c, with a= 13. 782(3), b= 18. 381(4), c= 16. 643(2) A, β= 92. 84(5)°, V=4211. 1 (4) A3, Z=4, Mr= 887. 03, Dc= 1. 40 g/cm3, μ= 5. 0 cm-1, F(000) = 1836 and R(Rw) = 0. 057(0. 062) for 2134 unique reflections with I> 3δ(I). Crystal (B) is also monoclinic, space group C2/c ,with a= 13. 793(4), b= 18. 401 (6), c= 16. 657(5) A’, β= 93. 18(3)°, V=4221. 3(5) A3, Z= 4, Mr=890. 88, Dc= 1. 40 g/cm3, μ= 10. 5 cm-1, F(000) = 1844 and R(Rw) = 0. 067 (0. 069) for 2131 unique reflections with I>3δ(I). Both (A) and (B)have been characterized by IR spectra. Besides, the relations between the structuresand IR are discussed.

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.

Synthesis and Crystal Structure of Tris(N-p-methylphenyl-3-hydroxy-2-ethyl-4-pyridinonato)iron(III)

The complex [Fe(C14H14NO2)3]2H2O has been prepared by reaction of N-p-methylphenyl-3-hydroxy-2-ethyl-4-pyridinone with FeCl36H2O. A single-crystal X-ray study shows that the iron atoms lie in a trigonally distorted octahedral environment coordinated to the hydroxy and ketone oxygen atoms of three ligands in the mer configuration Mr=773.57(C42H46N3O8Fe). The crystal is hexagonal with space group P31c; a=15.943(2), c=17.612(4)? V=3877.0(12)?, Z=4, Dc=1.325g/cm3, m=0.445mm-1, F(000)=1634, R=0.0446, wR= 0.1154 for 3085 reflections with I >2s(I). The bond lengths from iron to oxygens are 1.980(1)?for the ketone oxygens and 2.071(1)?for the hydroxy oxygens. The molecule exhibits the expected propeller shape, and the angle of the trigonal twist is 48.37. The dihedral angles are 0.5(2)?between chelate ring plane and pyridine ring plane and 71.31(7)?between pyridine ring plane and benzene ring plane. The solvent H2O(O(3) and O(4)) molecules are linked with O(2) and O(1) by hydrogen bonds with bond lengths 2.900(1) and 2.999(1)? respectively.

Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline (sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [sec-butylphenH][FeCl4]. UV-vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

Density Functional Theory Study on the First Hyperpolarizabilities of Mono-and Bimetal Ir(Ⅰ)/Rh(Ⅰ)2,2'-Bidipyrrins Complexes

Metal complexes with excellent nonlinear optical（NLO） properties have attracted considerable attention. The geometry structure, electronic spectra and NLO properties of 2,2？-bidipyrrins（L） and mono-and bimetal Ir（I）/Rh（I）–L complexes have been investigated by density functional theory method. Our calculations revealed that L with planar configuration shows the largest first hyperpolarizability value, which is 2.2 to 5.5 times larger than that of others. It is attributed to the single direction of intramolecular charge transfer. When metal ions were embedded in ligands, the first hyperpolarizability values of mono-and bimetal Ir/Rh（I）–L complexes were smaller than that of L, and that of bimetal Ir/Rh（I）–L complexes were smaller than the corresponding monometallic Ir/Rh（I）–L. This is caused by the intramolecular charge transfer from multiple directions as well as the amount of charge transfer. On the other hand, on increasing the number of metal ions, the charge transfer in the opposite direction cancels each other more obviously. Our work would provide some theoretical reference for the second-order NLO responses of mono-and bimetal complexes.

Synthesis, Crystal Structure and Thermal Behavior of a 3-D Barium(II)/Iron(III)-Oxalate Polymer

Reaction of Ba(NO3)2 with Fe(NO3)3·9H2O and H2C2O4·2H2O in aqueous medium readily affords, in high yield, the bimetallic complex polymer of chemical composition {Ba6(H2O)17[Fe(C2O4)3]4}·7H2O (1), consistent with the expected ratio of 3BaII vs. 2FeIII. Compound 1 was fully characterized by elemental and thermal analyses, vibrational FTIR spectroscopy, and by single crystal X-ray structure determination. The bulk structure of 1 is a 3-D metal-organic framework held together by intermetallic linkages across oxalate and aqua oxygen bridgings. Thermal analyses of 1 show significant weight losses corresponding to water molecules (lattice and coordinated), followed by the decomposition of the network.

FERROMAGNETICALLY COUPLED Gd(III)Cu(II)Gd(III)TRINUCLEAR COMPLEXES

Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.

Removal of Chromium(III) from the Waste Solution of an Indian Tannery by Amberlite IR 120 Resin

The extraction of chromium(III) from a model waste solution and also from a waste solution of an Indian tannery with Amberlite IR 120 resin is described, and the performance of this resin is compared with other similar resins. The parameters that were optimized include effect of mixing time, pH, loading and elution behaviours of chromium(III) for this resin. Sorption of chromium(III) on Amberlite IR 120 followed Freundlich isotherm and Langmuir isotherm model, and the maximum sorption capacity was determined to be 142.86 mg Cr(III)/g of the resin. Higher Freundlich constant (Kf) values (6.30 and 13.46 for aqueous feed of 500 and 1000 ppm Cr(III)) indicated strong chemical interaction through ion exchange mechanism of the metal ion with the resin. The kinetic data showed good fit to the Lagergren first order model for extraction of chromium(III). Desorption of chromium(III) from the loaded resin increased with the increase in concentration of eluent (5-20% H2SO4). With 20% (v/v) sulphuric acid solution 94% chromium(III) was eluted in three stages. Elution of the Cr(III) in the column experiments was however, found to be lower (82%) than that of the shake flask data. In case of Indian tannery’s waste solution, it was observed that almost total chromium was extracted in four stages with Amberlite IR 120.

A Chiral Three Dimensional Potassium(I)/Strontium(II)/Chromium(III) Oxalato-Bridged Coordination Polymer: Synthesis, Characterization and Thermal Analysis

A new compound of general formula {[(H2O)2K(μ-H2O)Sr]@[Cr(C2O4)3]}n (1) has been synthesized in water and characterized by elemental and thermal analyses, EDX, IR and UV-Vis spectroscopies and by single crystal X-ray structure determination. Compound 1 crystallizes in the chiral space group Fdd2 of orthorhombic system with a = 14.110 (4) ?, b = 36.074 (11)?, c =11.034 (3)? and Z = 16. Compound 1 is a coordination polymer in which the three-dimensional lattice framework is realized by the interconnectivity between K+ cations, Sr2+ cations, aqua ligands and [Cr(C2O4)3]3– complex anions. The asymmetric unit of 1 consists of one cationic motif formally written [(H2O)2K(μ-H2O)Sr]3+ and one anionic entity, [Cr(C2O4)3]3–. The K+ and Sr2+ ions in the cationic motif are both eight-coordinate while the Cr3+ ions in the anionic complex are six-coordinate in a distorted octahedral geometry. Coulombic interactions between the ionic motifs and the three-dimensional H-bonding involving aqua ligands help to consolidate the bulk structure. Thermogra-vimetric analysis (TGA) shows that compound 1 is stable to heat up to ca. 80℃.

SVNTHESES AND CHARACTERIZATION OF TWO HIGH VALENCE VANADIUM COMPLEXES (?) SCHIFF-BASE LIGAND WITH RICH PHENOLATE OXVGEN AND THEIR CONVERSION

Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.

复杂多径下IR-UWB自适应频偏估计算法研究

在脉冲超宽带定位系统中,时钟频率偏移是影响测距和测角精度的重要因素;针对复杂多径下频偏估计精度低的问题,设计了一种适应复杂多径环境的脉冲超宽带自适应频偏估计算法;首先,借助脉冲超宽带信号的抗多径优势,将实时估计的信道脉冲响应作为自适应匹配滤波模板,以保证复杂多径下相关峰的准确提取;利用相关峰辐角信息得到前导符号的相位序列;再使用贝叶斯估计算法提高频偏估计精度;在IEEE 802.15.4a标准CM1、CM2多径信道下进行仿真,仿真结果表明,低信噪比情况下,频偏估计精度保证在0.2 ppm以内;在巷道环境实验结果表明,50 m范围内频偏估计标准差在0.06 ppm以内;实现了复杂多径环境下高精度频偏估计,具有较强的实用性。

PRELIMINARY STUDIES ON THE SYNTHESIS AND CHARACTERIZATION OF OXY-AND THIO-DIACETIC ACID HYDRAZITION AND THEIR FIRST-ROW TRANSITION METAL COMPLEXES

It has been made certain that thio-and oxy-diacetic acid hydrazides are potential anticancer compounds.However,their ability to form complexes with transition metals and the properties of the complexes thus formed have not been studied.Employing a new potential anticancer ligand 1,2-bis(thioacetic acid hydrazide)ethane prepared in our lab,along with ligands oxydiacetic hydrazide and 1,2-bis(oxyacetic acid hydrazide) ethane,a series of 11 new first-row transition metal(M=Zn^(2+),Cu^(2+),Co^(2+), Ni^(2+))complexes with each of the above three ligands have been synthesized and characterized by means of elemental analyses,IR,TG and X-ray powder diffraction.

Synthesis,crystal structure and photo-physical properties of tris(4-methyl-2,5-diphenylpyridine)iridium for OLED

Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent materials.In this paper,Ir(bmppy)_(3),tris(4-methyl-2,5-diphenylpyridine)iridium,was synthesized and elvaluted for photo-physical characteristics.Single crystals suitale for X-ray diffraction(XRD)were grown from a mixture solvent of dichloromethane and absolute ethanol.The composition and structur of Ir(bmppy)_(3)were determined by element analysis,NMR spectra and XRD.The complex crystallizes in the monoclinic symmetry with the space group P21/c with a slightly distorted octahedral configuration.As measured by UV-Visible and photoluminescence spectra,Ir(bmppy)_(3) displays a maximum emission at at 527 nm at ambient temperature,a typical green-emitting profile.The complex has potential for application in the OLED industry.

基于Ir(Ⅲ)有机金属模块的三角双锥分子笼配位组装

采用亚组分自组装方法,构建了基于Ir(Ⅲ)有机金属模块的异核多金属Zn_(3)Ir_(2)构型配位超分子笼.通过核磁共振氢谱、质谱以及X射线单晶衍射对Zn_(3)Ir_(2)的分子结构进行了表征.Ir-Ir距离约为1.17nm,Zn-Zn距离约为0.78nm.Zn_(3)Ir_(2)分子笼结构中有一个较大且略微扭曲的矩形窗口,尺寸为0.79nm×0.75nm.所获得的Zn_(3)Ir_(2)分子笼具有优异的磷光发射能力和限域空腔微环境,在分子识别、光催化和药物递送等领域具有良好的应用前景.

九配位钇(III)-氨三乙酸配合物K_3[Y(NTA)2(H2O)]·6H_2O的合成及分子结构

：In this paper we describe the molecular and crystal structures of the K3[Y(NTA)2(H2O)]· 6H2O(H3NTA=nitrilotriacetic acid). The crystal data are as follows: monoclinic system, C2/c space group, a=1.5268(3)nm,b=1.2833(3)nm,c=2.6079(5)nm,β =96.03(3)° ,V=5.0815(18)nm3,Z=8,M=708.68,Dc=1.852gcm-3,μ =2.875mm-1,F(000)=2880.The final R1 and wR2 are 0.0636 and 0.1523 for 4264 [I >2.0σ (I)] unique reflections and 0.1178 and 0.1651 for all 4364 reflections,respectively.In the title complex, the anion [Y(NTA)2(H2O)]3- has a nine-coordination structure with distorted monocapped square antiprism. Each group acts as a tetradentate ligand with three O atoms and one N atom and a H2O molecule caps a quadrilateral face as a ligand.It can be known that the Y(III) ion can form a high-coordinate compound with aminopolycarboxylic acid ligands because it has a larger ionic radius (0.104nm).

壳聚糖膜与Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)复合物的IR光谱和XPS谱

将壳聚糖制成膜后浸泡在含有金属离子 Cu( )、Co( )、Ni( )的溶液中制备得到相应的复合物。根据 IR光谱中官能团特征频率的位移和 XPS谱中元素结合能的变化 ,表明 Co( )、Ni( )、Cu( )与壳聚糖膜的吸附机理包括物理作用和化学吸附 ,其中化学吸附是通过壳聚糖表面部分 - NH2 提供孤对电子和金属离子形成了配位键。

九配位(NH_4)_3[Y^III(ttha)]·5H_2O配合物的合成及结构

报道了含有自由羧酸基的新型稀土金属离子YIII氨基多羧酸配合物的合成及分子结构和晶体结构的测定 .具体结果如下 :分子式 (NH4 ) 3 [YIII(ttha) ]·5H2 O(ttha =三乙四胺六乙酸 ) ,单斜晶系 ,P2 (1) /c空间群 ,a =1.0 2 89(2 )nm ,b =1.2 75 7(3)nm ,c=2 .3184(5 )nm ,β =90 .92 (3)°,V =3.0 42 7(11)nm3 ,单位晶胞中的分子数为 4,Dc=1.5 75g·cm-3 ,μ =2 .0 0 2mm-1和F(0 0 0 ) =15 12 ,对 5 145个独立的衍射点它的R和Rw值分别为 0 .0 5 14和 0 .12 87,对所有5 2 85个衍射点它的R和Rw值分别为 0 .10 85和 0 .140 7.在配合物离子 [YIII(ttha) ]3 -中 ,YN4 O5部分是九配位变形的单帽四方反棱柱体结构 .其中的COO-是一个未参与配位的可用于修饰的自由羧酸基 .由此可知90 YIII ttha配合物通过修饰与具有定向功能的生物大分子等相接可形成定向放射性抗肿瘤药物 .

镝(III)与酰腙及1,10菲啰啉多元配合物的晶体结构及荧光性质

在水乙醇混合体系中 ,首次得到 2 羰基丙酸水杨酰腙 (C10 H10 N2 O4) ,1,10 菲啉 (C12 H8N2 ,简写作phen)与Dy(NO3 ) 3 ·3H2 O的配合物 [Dy(C10 H8N2 O4) (phen) (NO3 ) (H2 O) 2 ]·H2 O .该配合物属单斜晶系 ,空间群为P2 1/c,晶胞参数a =1 5 2 4( 3 )nm ,b =1 10 18( 19)nm ,c =1 468( 3 )nm ,β =92 2 8( 2 )° ,V =2 4 63 ( 7)nm3 ,Z =4,μ =3 10 0mm-1,Dc=1 83 1g/cm3 ,F( 0 0 0 ) =13 40 ,R =0 0 3 14 ,wR =0 0 660 ,GOF =0 966.测试结果表明 ,该单晶结构为镝的 9配位配合物 ,其中一个 2 羰基丙酸水杨酰腙分子以羧基氧、酰胺基中的羰基氧和CN中的氮与Dy3 + 三齿配位 ,形成两个稳定的共边五元环 ,一个 1,10 菲啉分子以二齿方式配位、一个硝酸根和两个水分子也同时参与配位 ,在空间呈扭曲的单帽四方反棱柱 ,而在配合物周围还有一个游离的水分子 .