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。     

钇二氢化反应热力学函数的研究

用密度泛函方法B3LYP/SDD/6-311＋＋G**计算了YH₂的微观性质. 并用分子总能量中的振动能E_v代替固态能量0705212, 振动熵S_Ev代替固态熵的近似方法, 以及考虑到电子能量的变化, 计算了固态YH₂(D, T)的焓H和熵S, 得到不同温度下Y与H₂, D₂, T₂反应的ΔH^⊖, ΔS^⊖, ΔG^⊖及氢化反应平衡压力, 导出了与温度的依赖关系. 计算结果表明, YH₂(s)的生成热为199.25 kJ•mol^－1, 与实验值210.00及 225.94 kJ•mol^－1非常接近, 说明近似方法的正确性.     

α-取代氨基氟代苯基膦酸酯衍生物的合成、晶体结构与抗癌活性

利用席夫碱与亚磷酸酯反应, 合成了新型O,O'-二烷基-α-(6-甲氧苯并噻唑-2-基氨基)-4-氟苯基膦酸酯化合物, 结构经元素分析, IR, ¹H NMR, ¹³C NMR和X单晶衍射确认. X单晶衍射测试结果表明: 化合物3d分子属于四面体晶系, 空间群I4(1)/a, a＝2.1055(3) nm, b＝2.1055(3) nm, c＝2.0521(5) nm, α＝90.00°, β＝90.00°, γ＝90.00°, V＝0.9098(3) nm³, Z＝16, D_c＝1.321 mg/m³, ＝0.250 mm^－1, F(000)＝3808. 化合物还存在着1个分子内氢键[N(2)—H(2)…O(1)]. 生物测定表明化合物3f在20 g/mL浓度下对PC3细胞的抑制率为84.3%.     

稀土配合物[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3的标准生成焓及热分解动力学研究

合成了高氯酸镨和咪唑(C₃H₄N₂), DL-α-丙氨酸(C₃H₇NO₂)混配配合物晶体. 经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃. 使用具有恒温环境的溶解-反应量热计, 以2.0 mol•L^－1 HCl为量热溶剂, 在T＝(298.150±0.001) K时测定出化学反应PrCl₃•6H₂O(s)＋2C₃H₇NO₂(s)＋C₃H₄N₂(s)＋3NaClO₄(s)＝[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃(s)＋3NaCl(s)＋5H₂O(1)的标准摩尔反应焓为Δ_rH_m^ө＝(39.26±0.11) kJ•mol^－1. 根据盖斯定律, 计算出配合物的标准摩尔生成焓为Δ_fH_m^ө{[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃(s), 298.150 K}＝(－2424.2±3.3) kJ•mol^－1. 采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学, 运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析, 求得分解反应的表观活化能E＝108.9 kJ•mol^－1, 动力学方程式为dα/dt＝2(5.90×10⁸/3)(1－α)[－ln(1－α)]^－1exp(－108.9×10³/RT).     

配合物Zn(Met)SO4•H2O(s)的低温热容和标准摩尔生成焓

利用精密自动绝热热量计直接测定了配合物Zn(Met)SO₄•H₂O(s) 在78～370 K温区的摩尔热容. 通过热容曲线的解析得到该配合物的起始脱水温度为T₀＝329.50 K. 将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容 (C_p,m)对温度(T)的多项式方程, 并且在此基础上计算出了它的舒平热容值和各种热力学函数值. 依据Hess定律, 通过设计热化学循环, 选择体积为100 cm³、浓度为2 mol•L^－1的盐酸作为量热溶剂, 利用等温环境溶解-反应热量计, 测定和推算出该配合物的标准摩尔生成焓为Δ_fH_m⁰＝－(2069.30±0.74) kJ•mol^－1.     

4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉的一步合成

报道了用3-甲酰基色酮、5,5-二甲基-1,3-环己二酮、乙酰乙酸乙酯与醋酸铵一步法合成4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉类化合物, 对其结构进行了表征, 并分析了代表性化合物2f的晶体结构. 2f晶体属于单斜晶系, P2/c空间群, 所得晶胞参数为: a＝2.0255(4) nm, b＝0.9132(2) nm, c＝1.4066(3) nm, β＝121.60(3)°, V＝2.2159(8) nm³, Z＝4, D_c＝1.335 g/cm³, μ＝0.209 mm^－1, F(000)＝736, R₁＝0.0556, wR₂＝0.1248.     

IIB族金属二硫代氨基甲酸配合物的合成、表征及热稳定性研究

在甲醇溶液中合成了一系列IIB过渡金属Zn(II), Cd(II)的二羟乙基二硫代氨基甲酸[(EtOH)₂dtc]的配合物, 并对配合物M[(EtOH)₂dtc]₂L [M＝Zn (1), Cd (2), L＝2,2'-联吡啶; M＝Zn (3), Cd (4), L＝邻菲啰啉]进行了红外光谱、元素分析、热重分析表征工作. 热重分析表明配合物1～4中DTC配体比中性配体更易失去, 热分解最终产物为相应的氧化物. 对化合物1, 2做了X-ray单晶衍射分析, 1为单斜晶系, P2₁/c空间群, 晶胞参数a＝0.72146(5) nm, b＝2.61720(18) nm, c＝1.59438(11) nm,b＝97.899(2)°, V＝2.9820(4) nm³, Z＝4, m＝1.133 mm^－1, D_c＝1.297 Mg•m^－3; 2为三斜晶系, P-1空间群, 晶胞参数a＝1.0075(2) nm, b＝1.1580(2) nm, c＝1.1777(2) nm, a＝70.92(3)°, b＝85.71(3)°, γ＝81.02(3)°, V＝1.2822(4) nm³, Z＝2, m＝2.118 mm^－1, D_c＝1.630 Mg•m^－3.     

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.     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

硫杂杯[4]芳烃氧化膦衍生物的合成与晶体结构

合成了部分取代的硫杂杯[4]芳烃氧化膦衍生物, 二(亚甲基二苯基氧化膦)对叔丁基硫杂杯[4]芳烃(化合物1), 培养了化合物的单晶, 用Smart 1000 CCD衍射仪测定了其晶体结构. 结果表明, 1的组成为: C₆₆H₇₀O₆P₂S₄•2CH₃OH, 属三斜晶系, P1空间群, 晶胞参数a＝1.3453(6) nm, b＝1.5289(7) nm, c＝1.7893(9) nm; α＝75.707(9)°, β＝69.131(8)°, γ＝79.734(9)°, Z＝2; V＝3.316(3) nm³, d＝1.215 g/cm³, F(000)＝1288, μ (Mo Kα)＝0.244 mm^－1, R₁＝0.0625, wR₂＝0.1372. 杯芳烃分子采取了锥式构象.     

烟酸的低温热容和标准摩尔生成焓

利用精密自动绝热热量计测量了分析纯烟酸在78～400 K温区的低温热容. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到了热容随温度变化的多项式方程. 用此方程进行数值积分, 得到在此温区每隔5 K的舒平热容值和相对于298.15 K时的热力学函数值. 利用精密静止氧弹燃烧热量计测定了烟酸在298.15 K时的恒体积燃烧能为 Δ_cU＝ －(24528.3±16.1) J•g^－1. 依据物质燃烧焓定义计算出烟酸的标准摩尔燃烧焓为: Δ_cH_m^o＝－(3019.05±1.98) kJ•mol^－1. 最后, 依据Hess定律计算出烟酸的标准摩尔生成焓为: Δ_fH_m^o＝－(56.76±2.13) kJ•mol^－1.     

多氯联苯醚的结构参数和热力学性质的密度泛函理论研究

采用密度泛函理论(DFT)方法在B3LYP/6-31G*水平上对209个多氯联苯醚(PCDEs)系列化合物进行了全优化和振动分析计算, 得到各分子的结构参数和热力学性质, 并研究了这些参数与氯原子的取代位置及取代数目(N_PCS)之间的关系. 结果表明: 分子平均极化率(α)、焓(H^Ө)、自由能(G^Ө)、恒容热容( )和熵(S^Ө)与N_PCS之间有很强的相关性(相关性系数r²分别为0.9955, 1.0000, 1.0000, 0.9918, 0.9995), 分子体积(V_m)和最高占据轨道能(E_HOMO)与N_PCS也有较好的相关性, 相关性系数r²分别为0.9735和0.9362. 设计等键反应, 计算了PCDEs系列化合物的标准生成热(Δ_fH^Ө)和标准生成自由能(Δ_fG^Ө). 根据异构体自由能的相对大小, 从理论上求得异构体的相对稳定性顺序.     

1-亚甲基苯并咪唑-1,4,7-三氮环壬烷配体及其铜配合物[Cu(C14H21N5)Br]2•[CuBr4]的合成与晶体结构

采用新的方法合成了1-亚甲基苯并咪唑-1,4,7-三氮环壬烷配体, 利用该配体合成了一个新的铜配合物[Cu(C₁₄H₂₁N₅)Br]₂•[CuBr₄] ([Cu(C₁₄H₂₁N₅)Br]^＋•[CuBr₄]^2－•[Cu(C₁₄H₂₁N₅)Br]^＋), 并测定了它的晶体结构, 结果表明: 该配合物的晶体属于单斜晶系的C2/c空间群, 晶胞参数a＝1.96209(15) nm, b＝0.82319(5) nm, c＝2.39249(15) nm, α＝90.00°, β＝102.996(2)°, γ＝90.00°, V＝3.7653(4) nm³, Z＝4, μ(Mo Kα)＝8.083 mm^－1, D_c＝2.097 Mg/m³, F(000)＝2308, R＝0.0417, wR＝0.0945, GOF＝0.933. 该配合物由两个1-亚甲基苯并咪唑-1,4,7-三氮环壬烷一溴合铜配阳离子和一个四溴合铜配阴离子组成. 在两个配阳离子中, 每个Cu(II)离子与五个配位原子配位(四个氮原子和一个溴阴离子), 位于一个变形四方锥的中心. 在配阴离子中, Cu(II)离子与四个溴阴离子配位, 位于一个稍变形四面体的中心.     

Excess properties and spectroscopic studies of binary system 1,4-butanediol + water at T = (293.15, 298.15, 303.15, 308.15, 313.15 and 318.15) K

Density and dynamic viscosity data were measured over the whole concentration range for the binary system 1,4-butanediol (1) + water (2) at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K as a function of composition under atmospheric pressure. Based on density and dynamic viscosity data, excess molar density (ρ^E), dynamic viscosity deviation (Δν) and excess molar volume (V_m^E) were calculated. From the dynamic viscosity data, excess Gibbs energies (ΔG*^E), Gibbs free energy of activation of viscous flow (ΔG*), enthalpy of activation for viscous flow (ΔH*) and entropy of activation for viscous flow (ΔS*) were also calculated. The ρ^E, V_m^E, Δν and ΔG*^E values were correlated by a Redlich?Kister-type function to obtain the coefficients and to estimate the standard deviations between the experimental and calculated quantities. Based on FTIR and UV spectral results, the intermolecular interaction of 1,4-butanediol with H₂O was discussed.     

Synthesis,Crystal Structure and Thermochemical Properties of a One‐Dimensional Chain Complex [Cd(succ)PIP]n

A new complex, [Cd(succ)PIP]_n (PIP=2‐phenyl‐imidazo[4,5‐f]1,10‐phenanthroline, H₂‐succ=succinate), was synthesized and characterized by X‐ray crystallography, elemental analysis, and TG‐DTG. The results show that the complex crystallizes in an orthorhombic space group Pcca; a=14.065(2) Å, b=9.901(8) Å, c=28.933(2) Å and Z=8. The structure of the complex is one‐dimensional chain [Cd(succ)PIP]_n, and each Cd²⁺ is five‐coordinated by two chelating nitrogen atoms from one PIP ligand, three oxygen atoms from three different succ dianionic ligands to form a distorted trigonal‐bipyramida geometry. The constant‐volume combustion energy of the complex, Δ_cU, was determined by an intelligent micro‐rotating‐bomb calorimeter (IMRBC‐type I) at 298.15 K. Then the standard molar enthalpy of combustion, Δ_cH_m^?, and the standard molar enthalpy of formation, Δ_fH_m^? have been calculated.     

A thermochemical study of the coordination reactions of La(III) with alanine and glycine

The solid-state coordination reactions of lanthanum chloride with alanine and glycine, and lanthanum nitrate with alanine have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L^-1 HCl solvent of these three solid-solid coordination reactions have been measured using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies have been determined to be Δ_f H _m ^θ[La(Ala)₃Cl₃·3H₂O(s), 298.2 K]= -3716.3 kJ mol^-1, Δ_f H _m ^θ [La(Gly)₃Cl₃·5H₂O(s), 298.2 K]= -4223.0 kJ mol^-1 and Δ_f H _m ^θ [La(Ala)₄(NO₃)₃·H₂O(s), 298.2 K]= -3867.57 kJ mol^-1, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermochemistry of inorganic sulfur compounds III. The standard molar enthalpy of formation at 298.15 K of US1.992 (β-uranium disulfide) by fluorine bomb calorimetry

A thoroughly analyzed specimen of β-uranium disulfide of composition US_1.992±0.002 has been studied by fluorine-bomb calorimetry. The standard molar energy of combustion: Δ_cU_m^o(US_1.992, cr, β, 298.15 K) = ?(4092.5±7.5) kJ·mol^?1 has been determined on the basis of the reaction: US_1.992(cr, β) + 8.976F₂(g) = UF₆(cr) + 1.992F₆(g). The standard molar enthalpy of formation: Δ_fH_m^o(US_1.992, cr, β, 298.15 K) = ?(519.7±8.0) kJ·mol^?1 was derived, and from that result Δ_fH_m^o(US₂, cr, 298.15 K) = ?(521±8) kJ·mol^?1 is estimated.     

原子价壳层电子量子拓扑指数与元素电负性的关系

在基态原子价壳层电子隐核图的基础上, 基于拓扑化学原理以及原子价壳层电子结构特征, 构建了原子价壳层电子量子拓扑指数(AEI), 它对基态原子实现唯一性表征, 结合原子价壳层电子平均化能(∑n_iE_i/∑n_i)等参数, 建立了一套新的元素电负性标度: X_N＝－0.588710AEI₁＋0.761214AEI₂＋0.154982(∑n_iE_i/∑n_i)－0.080929. 该式给出了周期表中氢至镅共95种元素的电负性, 结果表明新电负性标度X_N与Pauling电负性标度颇为一致. 进一步从原子价轨道量子拓扑指数确定了sp, sp², sp³杂化轨道的电负性. 新标度在元素和物质的结构-性质研究中具有一定的适用性.