价电子能级连接性指数及其应用

价电子能级连接性指数( ^fE)被定义为： ^fE=Σ(m_i·m_j…)^-0.5,m为价电子能级值。其中0、1阶指数公式分别为： ⁰E=Σ(m_i)^-0.5、 ¹E=Σ(m_i·m_j)^-0.5。 ⁰E、 ¹E与化合物的总键能(ΔE)、晶格能(U)、标准生成焓(Δ_fH^?_m)以及非金属氢化物的pKa呈现高度相关性。它们的线性回归方程为：ΔE=-48.0095+1402.9463¹E,r=0.9474, U=-328.0770+1541.9351 ¹E, r=0.9801,-Δ_fH^?_m=-266.9299+1324.6461 ¹E, r=0.9509, pKa=-20.9723+28.1756 ¹E, r=0.98884, pKa=-14.6102-7.835 ⁰E+40.6461 ¹E, R=0.9933。m、^fE具有物理意义明确、计算方法简单等优点,而且预测结果令人满意。     

一种电负性新标度：基态自由原子价壳层电子平均吸引能

原子吸引价电子的总能力可由基态自由原子的价电子离子化能(TIE=Σn_iE_i)及其电子亲合能(EA)之和来度量。该和值亦称为总吸引能,记为TAE=Σn_iE_i+EA,此处E_i为基态自由原子价壳层电子的离子化能,Σn_i为与之相关的价壳层电子数,EA则是电子亲合能。所指出的新电负性标度χ_CL与总吸引能TAE除以原子价壳层电子数目Σn_i之值即平均吸引能成正比：χ_CL=0.1813 AAE=0.1813 TAE/Σn_i=0.1813(Σn_iE_i+EA)/Σn_i,进一步从原子总吸引能TAE可确定其价轨道电负性。     

电性指数、电性连接性指数及其应用

In this paper the electric index (f_i) of combined atom is defined as f_i=m²_i·x_pi·(n^*_i)^-0.5. f_i has defineated the primary factors to affect hydrated heat of metal ion (ΔH_h) and solubility of metal hydroxide (pK_m). Their relation formulas are set up by least square method: -ΔH_h=260.31+519.31f_i, n′=51, r=0.9693; pK_m=0.0285+1.1358f_i, n′=46, r=0.9642. The calculated values of pK_m are better than the documental method. The electric connectivity index ( ^mF) is built up with f_i, and among them the formulas of zero, first order index are defined as ⁰F=Σ(f_i)^0.5, ¹F=Σ(f_i·f_j)^0.5 respectively. ⁰F and ¹F have highly correlativity for lattice energies (U) of inorganic compounds. Their linear regression equations are proposed as follows: (1) for 47 inorganic compounds, U=-228.41+407.62⁰F+169.38¹F, R=0.9985; (2) for 34 main group compounds, U=-420.39+507.72⁰F+144.96¹F, R=0.9992; (3) for 13 transitional element halides, U=573.80-119.97⁰F+458.58¹F, R=0.9984. The predicting values by ⁰F and ¹F basically tally with the experiment values, and are even more ideal than the theoretical values of document.     

CH2(COO)2Cu·2H2O热分解的非等温动力学研究

The thermal dehydration and decomposition kinetics of CH₂(COO)₂Cu·2H₂O were investigated using the non-isothermal method by thermogravimetry (TG) technique in N₂. The iterative iso-conversional methods were applied to calculate the activation energy E_a of dehydration and decomposition， and the most probable mechanism function G(α) was determined by means of the master plots method. The pre-exponential factor A was obtained on the basis of E_a and G(α). Kinetic parameters (E_a and lnA) of dehydration were given as: E_a=139.79 kJ·mol^-1， ln(A/s^-1)=47.38. The mechanism function of the dehydration was G(α)=[-ln(1-α)]^2/3， and the decomposition of CH₂(COO)₂Cu proceeds to completion by two distinct reactions. These two reactions overlap in the transition process (0.45<α<0.65). Kinetic parameters (E_a and lnA )of the first reaction of decomposition were: E_a=201.15 kJ·mol^-1， ln(A/s^-1)=52.29， and the mechanism function was G(α)=[1-α]^-0.37. And in the second reaction G(α)=α+(1-α)ln(1-α)， E_a=156.74 kJ·mol^-1， ln(A/s^-1)=39.58.     

邻乙酰氨基苯甲酸、邻菲咯啉锌(Ⅱ)配合物的合成、晶体结构及性质研究

在甲醇水混合溶剂中,以邻乙酰氨基苯甲酸(o-ABA),1,10-邻菲咯啉(phen)为配体与高氯酸锌合成了标题配合物[Zn(o-ABA)(phen)₂](ClO₄)·0.5H₂O。配合物(C₆₆H₅₀N₁₀O₁₅C₁₂Zn₂,分子量为1 424.80)晶体属三斜晶系,空间群P1,晶胞参数：a=1.181 6(6) nm,b=1.635 6(8) nm,c=1.752 2(9) nm,α=95.733(9)°,β=93.083(8)°,γ=109.212(8)°;V=3.168(3) nm³,D_c=1.494 g·cm^-3,Z=2,F(000)=1 460。最终偏离因子R₁=0.048 2,wR₂=0.098 3。晶体结构表明：锌原子与1个对乙酰氨基苯甲酸的2个氧原子,2个1,10-邻菲咯啉中的4个氮原子配位,形成六配位的变形八面体结构。并对配合物的热稳定性,光谱及电化学性质进行了分析。     

二水·2-羰基丙酸水杨酰腙合铜(Ⅱ)配合物的晶体结构及生物活性

在水中,以2-羰基丙酸水杨酰腙与硫酸铜反应,制得新配合物Cu(C₁₀H₈N₂O₄)(H₂O)₂(C₁₀H₈N₂O₄^2-为2-羰基丙酸水杨酰腙负离子),并以水为溶剂培养了单晶,测试了晶体结构,该单晶为深绿色,属单斜晶系,空间群为C2/c,晶胞参数a=1.1297(1)nm,b=0.9824(8)nm,c=2.1973(3)nm,β=91.91(8)°,V=2.43749(8)nm³,Z=8,μ=1.817mm^-1,D_c=1.743Mg·m^-3,F(000)=1304,R=0.0264,wR=0.0654,GOF=1.052。其测试结果表明在配合物中Cu²⁺处于五配位的四方锥配位环境,配位原子分别来自1个三齿配体2-羰基丙酸水杨酰腙负二价离子的2个O原子和1个N原子,2个水分子中的O原子,其中1个水分子的O原子处于四方锥的锥顶,锥底的配位原子基本处于同一平面上。对该配合物所作的皿内抑菌试验和盆栽活体实验表明,配合物对小麦条锈病、白菜黑斑病及辣椒疫霉菌等分别有96%、89%、100%的抑制率,且有一定的助长作用。     

结构参数X的计算方法及与分子总键能和生成焓的关系

本文借助于电负性I和有效主量子数n_i^*定义了有效价电子数Z_i′。由Z_i′、 n^*_i及成键电子数mi定义的原子结构参数δ_i和分子结构参数X被计算。发现A_mB_n型分子的X相似文献   

［Mn2(CHZ)4(H2O)2］(PA)4·10H2O的制备和分子结构研究

本文论述了苦味酸(PA,三硝基苯酚)锰与碳酰肼(CHZ, NH₂NHCONHNH₂)反应制备目标配合物的方法及该配合物的晶体结构。该配合物的结构式为［O,O′-μ-Mn₂(CHZ)₄(H₂O₂)］(PA)₄·10H₂O。晶体属三斜晶系,P1 空间群。晶体学参数为：a=0.8269(1) nm, b=1.2812(1) nm, c=1.5915(1) nm; α=109.58(1)°, β=95.19(1)°, γ=92.76(1)°, V=1.5765(2)nm³; Z=1, Dc=1.580 g·cm^-3, μ(Mo K_α)=520 m^-1。晶体结构经全矩阵最小二乘法修正,最终偏离因子R=0.0557。该化合物为具有中心对称的双核配合物,以两个碳酰肼分子中羰基氧为桥原子将两个锰离子结合起来,与锰离子形成配位键的原子是碳酰肼分子第一、五氮原子,羰基氧原子和水分子中的氧原子,锰离子的配位数为七。若味酸根作为外界离子以库伦力和氢键与内界离子结合成配合物分子。     

含非交换氘的四唑-锌配合物

The solvothermal reaction (D₂O) of 2,6-dideuterium-4-cyanopyridine with ZnCl₂ in the presence of NaN₃ offers a novel complex Zn(OD)(C₆H₂D₂N₄) (1) in which Zn has a distorted tetrahedron composed of two N atoms from one tetrazoyl group and pyridyl group and two O atoms from two deuteratohydroxy OD groups. Crystal data for 1: Pbcn, a=1.456 8(5) nm, b=0.659 2(2) nm, c=1.645 3(5) nm, α=90°, β=90°, γ=90°, V=1.580 0(9) nm³, Z=8, M=231.54, D_c=2.236 Mg·m^-3, μ=3.070 mm^-1, R₁=0.043 4, wR₂=0.120 6, S=1.029. CCDC: 660629.