胺(或氨) - CHCl3系CT复合物密度泛函法研究

报道对氨(NH3母体)、甲胺(CH3NH2)、二甲胺[(CH3)2NH]、三甲胺[(CH3)3N]与三氯甲烷(CHCl3)形成的系列复合物的理论研究结果。把复合物看作一个超分子,在B3LYP/6-311G(d,p)的水平上进行密度泛函法计算,并运用完全均衡校正法进行基组超位误差校正(BSSE)。探讨该系列复合物的电子结构与相关性质,如稳定性、电荷转移及主要几何参数的变化规律等,结果表明,形成复合物的稳定性次序为NH3－CHCl3(Ⅰ)>CH3NH2-CHCl3(Ⅱ)>(CH3)2NH-CHCl3(Ⅲ)>(CH3)3N-CHCl3(Ⅳ)。形成复合物的过程包含着电荷转移。该系列复合物的稳定性与电荷转移量、前线轨道能量差△εL-H及广义H键距离良好的线性关系,与结合点的电荷布居也有密切的关系,复合物的稳定性是分子间共价作用和静电作用两方面因素综合的结果。计算结果能较好地解释有关的实验现象和规律。     

胺(或氨)一CHCI3系CT复合物密度泛函法研究

报道对氨(NH3,母体)、甲胺(CH3NH2)、二甲胺[(CH3)2NH]、三甲胺[(CH3)3N]与三氯甲烷(CHCL3)形成的系列复合物的理论研究结果．把复合物看作一个超分子,在B3LYP/6-311G(d,p)的水平上进行密度泛函法计算,并运用完全均衡校正法进行基组超位误差校正(BSSE).探讨该系列复合物的电子结构与相关性质,如稳定性、电荷转移及主要几何参数的变化规律等.结果表明,形成复合物的稳定性次序为NH3-CHCl3(Ⅰ)>CH3NH2-CHCL3(Ⅱ)>(CH3)2NH-CHCl3(Ⅲ)>(CH3)3N-CHCl3(Ⅳ).形成复合物的过程包含着电荷转移.该系列复合物的稳定性与电荷转移量、前线轨道能量差ΔεL-H及广义H键距离有良好的线性关系,与结合点的电荷布居也有密切的关系.复合物的稳定性是分子间共价作用和静电作用两方面因素综合的结果.计算结果能较好地解释有关的实验现象和规律.     

芳香氮化物-CHCl3系列复合物密度泛函法研究

报道对芳香氮化物吡咯(C4H5N)、苯胺(C6H5NH2)、对位氯代吡啶(C5H4NCl)、吡啶(C5H5N)及吡咯负离子(C4H4N-)与三氯甲烷(CHCl3)形成的系列弱作用复合物的理论计算结果.把复合物看作是一个超分子,在密度泛函B3LYP/6-311G(d,p)的水平上进行计算,探讨该系列复合物的稳定性规律、电荷转移及主要几何参数变化等规律.计算结果表明:此类芳香氮化物与三氯甲烷(CHCl3)可形成一系列弱化学作用复合物,特别是带负电荷的芳香氮化物可与CHCl3形成较稳定的复合物.形成复合物的过程包含着电荷转移,该系列复合物的稳定性与广义H键距离的变化规律相一致,与电荷转移量的变化规律大体一致.     

苯酚-酰胺系列氢键复合物从头计算研究

运用G94W量子化学程序包,在HF/6-31G基组水平上对酰胺(DMF,DMA,HCONH2,HCONHCH3andCH3CONH2)与苯酚形成的系列氢键复合物(看作超分子)进行从头计算研究。根据计算结果探讨复合物的稳定性、施体和受体间的电荷转移及几何参数变化等规律。结果表明苯酚与上述一系列酰胺都可形成稳定的氢键复合物,其稳定性次序为CH3CONH2～HCONHCH3＞HCONH2＞DMA＞DMF。结果还表明形成氢键复合物的过程包含着电荷转移,电荷由供体酰胺转移到受体苯酚中,酰胺中C=O键长和苯酚中的O-H键长都明显有规律性地变长。计算结果与实验规律相符。     

三硝基苯-对位取代苯酚负离子荷移复合物从头算研究

运用G94W量子化学程序,在HF/3-21G基组水平上对三硝基苯-对位取代苯酚(取代基:CH~3O-,CH~3-,Cl-)负离子的电荷转移复合物进行从头计算。把电荷转移复合物看成一个超分子,研究该系列复合物的稳定性、电荷转移及几何构型等规律。计算结果表明,苯酚负离子供电中心O沿一倾角指向三硝基苯中的任意相邻两个硝基之间的C位置上,复合物的稳定性按对位取代苯酚取代基CH~3O-,CH~3-,Cl-的次序减小,与实验规律相一致。计算结果还表明,形成该系列复合物具有明显的电荷转移,其稳定性与电荷转移量有关等。     

[(CH3)2NH2]3[NSiMo12O40]·2DMF·4H2O的合成和晶体结构

电荷转移盐;[(CH3)2NH2]3[NSiMo12O40]·2DMF·4H2O的合成和晶体结构     

螺桨烷型分子BX[(CH_2)_n]_3和BX(CH_2)[CH(CH_2)_nCH](X=N,P)的结构和性质

采用密度泛函理论(DFT)研究了螺桨烷型分子BX[(CH2)n]3和BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的结构、稳定性、化学键和电子光谱性质.计算结果表明这些分子都是稳定的.BX[(CH2)n]3(X=N,P;n=1-6)的最高占据分子轨道(HOMO)和最低空分子轨道(LUMO)之间的能隙均大于5.20 eV,其中BN[CH2]3和BP[CH2]3的能隙超过7.0 eV,与C5H6的能隙(7.27 eV)很接近,BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的能隙在6.80 eV左右.所研究分子能量的二阶差分表明BN[(CH2)3]3、BP[(CH2)4]3及BX(CH2)[CH(CH2)2CH](X=N,P)是最稳定的.BX[(CH2)n]3的Wiberg键级表明除了BN[(CH2)n]3(n=2和6)中不存在B―N键,其它化合物中B和N均形成了化学键,BP[(CH2)n]3中除了BP[(CH2)2]3不存在B―P键,其它的均存在.电子密度的拓扑分析表明N―B键属于离子键,而P―B键具有共价键特征.BX[(CH2)n]3(X=N,P)的第一垂直激发能分别在191.1-284.8 nm和191.8-270.1 nm之间,BX(CH2)[CH(CH2)n CH](X=N,P)的第一垂直激发能分别在190.5-199.7 nm和209.0-221.3 nm之间.     

两个基于[SMo_(12)O_(40)]~(2-)和冠醚基超分子阳离子的无机-有机杂化晶体的合成及晶体结构（英文）

以18-冠-6和4-碘-苯铵盐,二苯并30-冠-10和3-氟-4-氯-苯铵盐为超分子阳离子构建单元,分别引入到Keggin型[SMo_(12)O_(40)]~(2-)中,使用H管扩散法和溶剂挥发法合成了无机-有机杂化材料[(4-I-Anis)([18]crown-6)]2[SMo12O40]·CH3CN (1)和[(3-F-4-Cl-Anis)2(DB[30]crown-10)][SMo12O40]·2CH3CN (2)(4-I-Anis=4-碘-苯铵盐;3-F-4-Cl-Anis=3-氟-4-甲基苯铵盐;DB[30]crown-10=二苯并30-冠-10)。通过红外光谱、元素分析、热重分析、固态漫反射光谱和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。晶体1中,在bc平面,每个[SMo_(12)O_(40)]~(2-)多酸阴离子被6个超分子阳离子(4-I-Anis)([18]crown-6)围绕,形成六边形的结构;晶体2中,在bc平面,每个[SMo_(12)O_(40)]~(2-)多酸阴离子被4个大的超分子阳离子(3-F-4-Cl-Anis)2(DB[30]crown-10)围绕,形成四边形的结构。热重分析表明,氢键在维持晶体1和2的稳定性上起着主要的作用。固态漫反射光谱表明,[SMo_(12)O_(40)]~(2-)和冠醚基超分子阳离子之间存在电荷转移作用。     

卤代硅烷(R3SiX)与NR''3形成五配位硅化合物的加成反应

对R3SiX(R=H、CH3;X=F、Cl、Br、I)与NR'3(R'=H、CH3)的加成物用量子化学密度泛函方法在B3LYP/6-31g(d,p)基组下(X原子采用cep-121g基组)进行了两种加成方式的研究.一种是NR'3沿Si-X键轴向位置的加成,另一种是NR'3沿Si-X键侧向接近的加成.计算结果表明,前者更稳定且更容易形成加成物;Si上斥电子基团不利于Si-N键的形成,而N上斥电子基团则有利于Si-N键的形成;NH3-H3SiX系列和N(CH3)H3-H3SiX系列均能以两种方式进行加成,NH3-H2(CH3)SiX系列仅能沿Si-X键轴向进行加成,而NH3H(CH3)2SiX和NH3-(CH3)3SiX系列两种方式都不能进行加成;在同系列加成产物中,以X=Cl时所得加成物最稳定.讨论了所有加成物中各键的性能、NBO电荷变化、取代基对加成物结构和稳定性的影响,并对H3SiX(X=F、Cl、Br、D与NH3及N(CH3)3加成物在有机溶剂中导电的可能性进行了讨论.     

卤代硅烷(R3SiX)与NR’3形成五配位硅化合物的加成反应

对R3SiX(R=H、CH3; X=F、Cl、Br、I)与NR’3 (R’=H、CH3)的加成物用量子化学密度泛函方法在B3LYP/6-31g(d,p)基组下(X原子采用cep-121g基组)进行了两种加成方式的研究. 一种是NR’3沿Si—X键轴向位置的加成, 另一种是NR’3沿Si—X键侧向接近的加成. 计算结果表明, 前者更稳定且更容易形成加成物; Si上斥电子基团不利于Si—N键的形成, 而N上斥电子基团则有利于Si—N键的形成; NH3-H3SiX系列和N(CH3)3-H3SiX系列均能以两种方式进行加成, NH3-H2(CH3)SiX系列仅能沿Si—X键轴向进行加成, 而NH3-H(CH3)2SiX和NH3-(CH3)3SiX 系列两种方式都不能进行加成; 在同系列加成产物中, 以X=Cl时所得加成物最稳定. 讨论了所有加成物中各键的性能、NBO电荷变化、取代基对加成物结构和稳定性的影响, 并对H3SiX(X=F、Cl、Br、I)与NH3及N(CH3)3加成物在有机溶剂中导电的可能性进行了讨论.     

Ab initio molecular orbital investigation of the amine-alanes (CH(3))(n)H(3)(-)(n)AlNX(3) and phosphane-alanes (CH(3))(n)H(3)(-)(n)AlPX(3) (X = H, F, and Cl; n = 0-3) complexes

We report on ab initio calculations at the G2(MP2) level of the structures and Al-N(P) bond complexation energies of the (CH(3))(n)H(3)(-)(n)AlNX(3) and (CH(3))(n)H(3)(-)(n)()AlPX(3) (X = H, F, and Cl; n = 0-3) donor-acceptor complexes. For the (CH(3))(3)AlNX(3) and (CH(3))(3)AlPX(3) complexes, the C(3)(v) symmetry is found to be favored, and for the other complexes the C(s) symmetry is found to be favored. The G2(MP2) calculated complexation energies show for the amine ligands the trend NH(3) > NCl(3) > NF(3). A similar trend PH(3) approximately PCl(3) > PF(3) is predicted for the phosphane ligands. The NBO partitioning scheme shows that there is no correlation between the stability and the charge transfer.     

Magnitude and directionality of the interaction energy of the aliphatic CH/pi interaction: significant difference from hydrogen bond

The CCSD(T) level interaction energies of CH/pi complexes at the basis set limit were estimated. The estimated interaction energies of the benzene complexes with CH(4), CH(3)CH(3), CH(2)CH(2), CHCH, CH(3)NH(2), CH(3)OH, CH(3)OCH(3), CH(3)F, CH(3)Cl, CH(3)ClNH(2), CH(3)ClOH, CH(2)Cl(2), CH(2)FCl, CH(2)F(2), CHCl(3), and CH(3)F(3) are -1.45, -1.82, -2.06, -2.83, -1.94, -1.98, -2.06, -2.31, -2.99, -3.57, -3.71, -4.54, -3.88, -3.22, -5.64, and -4.18 kcal/mol, respectively. Dispersion is the major source of attraction, even if substituents are attached to the carbon atom of the C-H bond. The dispersion interaction between benzene and chlorine atoms, which is not the CH/pi interaction, is the cause of the very large interaction energy of the CHCl(3) complex. Activated CH/pi interaction (acetylene and substituted methanes with two or three electron-withdrawing groups) is not very weak. The nature of the activated CH/pi interaction may be similar to the hydrogen bond. On the other hand, the nature of other typical (nonactivated) CH/pi interactions is completely different from that of the hydrogen bond. The typical CH/pi interaction is significantly weaker than the hydrogen bond. Dispersion interaction is mainly responsible for the attraction in the CH/pi interaction, whereas electrostatic interaction is the major source of attraction in the hydrogen bond. The orientation dependence of the interaction energy of the typical CH/pi interaction energy is very small, whereas the hydrogen bond has strong directionality. The weak directionality suggests that the hydrogen atom of the interacting C-H bond is not essential for the attraction and that the typical CH/pi interaction does not play critical roles in determining the molecular orientation in molecular assemblies.     

Ab initio studies of electron acceptor-donor interactions with blue- and red-shifted hydrogen bonds.

The features of blue- and red-shifted electron acceptor-donor (ACH/B) hydrogen bonds have been compared by using quantum chemical calculations. The geometry, the interaction energy and the vibrational frequencies of both blue- (ACH=F3CH, Cl3CH with B=FCD3) and red-shifted (ACH=F3CH, Cl3CH with B=NH3 and ACH=CH3CCH with B=FCD3, NH3) complexes were obtained by using ab initio MP2(Full)/6-31+G(d,p) calculations with the a priori basis-set superposition error (BSSE) correction method. One-dimensional potential energy and dipole moment functions of the dimensionless normal coordinate Q1, corresponding to the CH stretching mode of ACH, have been compared for both types of complexes. Contributions of separate components of the interaction energy to the frequency shift and the effect of electron charge transfer were examined for a set of intermolecular distances by using the symmetry-adapted perturbation theory (SAPT) approach and natural bond orbitals (NBO) population analysis.     

A gas- and condensed-phase density functional study of donor-acceptor complexes of sulfur trioxide

A series of donor-acceptor complexes containing sulfur trioxide have been studied in the gas and condensed phases using density functional theory. The condensed phase is represented using the polarizable continuum model. The systems investigated include complexes of nitrogen-containing donor molecules, (CH(3))(n)H(3-n)N (n = 0-3), with SO(3) and complexes of oxygen-containing donor molecules, (CH(3))(m)H(2-m)O (m = 0-2), with SO(3). Significant differences are observed between the gas- and condensed-phase properties of the complexes as a result of the ability of the condensed-phase medium to support higher charge separation between the donor and acceptor. The gas/condensed-phase behavior of two nitrogen-containing complexes, (CH(3))H(2)N-SO(3) and (CH(3))(2)HN-SO(3), has been investigated for the first time. These complexes exhibit properties intermediate to the previously observed H(3)N-SO(3) and (CH(3))(3)N-SO(3) complexes. Systematic trends in the gas- and condensed-phase structure and properties have been observed as methyl groups are added to the donor molecule. In addition, two oxygen-containing complexes, CH(3)OH-SO(3) and (CH(3))(2)O-SO(3), have been characterized for the first time. The differences between the gas- and condensed-phase properties of the oxygen-containing complexes are, in many cases, larger than those of the nitrogen-containing complexes, and therefore they represent an intriguing new class of complexes for potential experimental observation. Finally, a strong correlation between the charge transfer and binding energy has been obtained for both the nitrogen- and oxygen-containing complexes of sulfur trioxide.     

First example of the solid-state thermal cyclometalation of ligated benzophenone imine giving novel luminescent platinum(II) species

The (benzophenone imine)platinum(II) compounds trans-[PtCl2(Ph2C=NH)(RR'SO)] [R, R'=Me, Me (2); n-Pr, n-Pr (3); (CH2)4 (4); Me, Ph (5); Me, p-MeC6H4 (6)] were prepared by the reaction of Ph2C=NH with K[PtCl3(RR'SO)], obtained in situ from K2[PtCl4] and the corresponding sulfoxide, giving 2-6 as well as cis-[PtCl2(Ph2C=NH)2] (1) as a minor product. The complexes were characterized by 1H, 13C, and 195Pt NMR and IR spectroscopy, electrospray ionization mass spectrometry, and C, H, and N elemental analysis. The X-ray crystallography of 1 enables confirmation of the cis configuration of the complex, while in 2 and 4.1/2CHCl3, the imine and sulfoxide ligands are mutually trans. The solid-state structure of 4.1/2CHCl3 consists of two dimeric Pt moieties representing a rather weak Pt...Pt interaction. The dimeric architecture of 4.1/2CHCl3 is enhanced by the hydrogen bonding between imine H atoms and O atoms. The orthometalation of 1 and 2-6 proceeds both in the solid phase and in a toluene suspension, leading to the formation of [PtCl{Ph(C6H4)C=NH}(Ph2C=NH)] (7) and [PtCl{Ph(C6H4)C=NH}(RR'SO)] (8-12), respectively, isolated in nearly quantitative yields. Complexes 8-12 are emissive at room temperature both in solution (lambdaemmax approximately 535 nm) and in the solid state (lambdaemmax 560-610 nm), with excited-state lifetimes of ca. 300-600 ns, representing a new family of PtII-based luminescent complexes. Compounds 8 and 10 have been characterized by X-ray analysis, confirming the square-planar coordination geometry of the metal center with the almost planar platinacycles. In 8, the asymmetric unit contains two independent Pt molecules, while in 10, it includes four Pt molecules linked by the intermolecular hydrogen-bonding network between the NH group and Cl atoms.     

CH3SH…HOO开壳型氢键复合物的结构及其电子密度拓扑性质

在DFT-B3LYP/6-311++G**水平下求得CH3SH…HOO复合物势能面上的稳定构型. 计算结果表明, 在HOO以其O8—H7作为质子供体与CH3SH分子中的S5原子为质子受体形成的氢键复合物1和2中, O8—H7明显被“拉长”, 且其伸缩振动频率发生显著的红移, 红移值分别为330.1和320.4 cm-1; 在CH3SH分子以其S5—H6作为质子供体与HOO的端基O9原子为质子受体形成的氢键复合物3和4中, 也存在类似的情况, 但S5—H6伸缩振动频率红移不大. 经MP2/6-311++G**水平计算的4种复合物含BSSE校正的相互作用能分别为-20.81, -20.10, -4.46和-4.52 kJ/mol. 自然键轨道理论(NBO)分析表明, 在CH3SH…HOO复合物1和2中, 引起H7—O8键长增加的因素包括两种电荷转移, 即孤对电子n1(S5)→σ*(H7—O8)和孤对电子n2(S5)→σ*(H7—O8), 其中后者为主要作用. 在复合物3和4中也有相似的电荷转移情况, 但轨道间的相互作用要弱一些. AIM理论分析结果表明, 4个复合物中的S5…H7间和O9…H6间都存在键鞍点, 且其Laplacian量▽2ρ(r)都是很小的正值, 说明这种相互作用介于共价键和离子键之间, 偏静电作用为主.