同时基于氢键和卤键的尿素含碘衍生物对卤素阴离子的识别机理北大核心CSCD

采用密度泛函B3LYP(Becke,three-parameter,Lee-Yang-Parr)量子化学理论方法探讨了同时基于氢键和卤键者两种弱相互作用的尿素无氟含碘衍生物对卤素阴离子(F-,Cl-,Br-和I-)的识别机理,结果发现尿素衍生物受体分子A以其结构中的两个N-H键和两个C-I与卤素阴离子间形成四齿弱键进行识别.其中包括2个N-H…X-红移氢键和2个C-I…X-蓝移卤键弱相互作用.另外,经BSSE校正后的A…F-,A…Cl-,A…Br-和A…I-分子识别体系中相互作用能ΔECP分别为-48.90,-121.78,-311.42和-96.55kJ/mol,从结合强度上来看,受体A对Br-和Cl-具有较好的识别能力,而对F-的识别能力相对较弱.此外,采用自然键轨道(NBO)理论分析了C…X-(X=F-,Cl-,Br-和I-)识别体系中红移氢键和蓝移卤键的电子行为与性质.     

1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙钳形受体对卤素阴离子的识别机理

采用密度泛函B3LYP(Becke, three-parameter, Lee-Yang-Parr)和HF(Hatree-Fock)方法, 从理论上探讨了1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙(DAPHZ)钳形受体对卤素阴离子的识别机理,结果发现DAPHZ受体以其钳形结构中的-N-H基团与卤素阴离子间形成双侧红移氢键进行识别. 经BSSE校正后DAPHZ•••F-, DAPHZ•••Cl-和DAPHZ•••Br-体系的分子识别相互作用能ΔECP分别为-327.5,-163.5和-148.3 kJmol-1, 说明钳形DAPHZ受体对F-具有最好的识别能力. 此外, 采用自然键轨道(NBO)计算, 相关H原子化学位移计算及分子中原子(AIM)等理论分析了识别体系中红移氢键的电子结构和性质, 结果表明APHZ受体对卤素阴离子的识别能力的相对顺序为DAPHZ•••F- >> DAPHZ•••Cl- ≈ DAPHZ•••Br-.     

1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙钳形受体对卤素阴离子的识别机理

采用密度泛函B3LYP(Becke, three-parameter, Lee-Yang-Parr)和HF(Hatree-Fock)方法, 从理论上探讨了1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙(DAPHZ)钳形受体对卤素阴离子的识别机理,结果发现DAPHZ受体以其钳形结构中的-N-H基团与卤素阴离子间形成双侧红移氢键进行识别. 经BSSE校正后DAPHZ•••F-, DAPHZ•••Cl-和DAPHZ•••Br-体系的分子识别相互作用能ΔECP分别为-327.5,-163.5和-148.3 kJmol-1, 说明钳形DAPHZ受体对F-具有最好的识别能力. 此外, 采用自然键轨道(NBO)计算, 相关H原子化学位移计算及分子中原子(AIM)等理论分析了识别体系中红移氢键的电子结构和性质, 结果表明APHZ受体对卤素阴离子的识别能力的相对顺序为DAPHZ•••F- >> DAPHZ•••Cl- ≈ DAPHZ•••Br-.     

间-苯二氧乙酰-(N-苯甲酰基)肼钳形受体对卤素阴离子的识别机理

采用密度泛函B3LYP（Bccke.thrcc-paramctcr,Lee-Yang-Parr）方法探讨了间-苯二氧乙酰-（N-苯甲酰基）肼（DAPHZ）受体对卤素阴离子的识别机理,结果发现DAPHZ钳形受体C构型以其钳形结构中的N-H键与卤素阴离子间形成多齿红移氢键进行识别,其中C…X^-（X=F^-,Cl^-和Br^-）体系中主客体间以双齿氢键识别结合,而在C…I^-体系中主客体间以三齿氢键识别结合,说明钳形受体C对I^-在空间几何上具有最好的匹配性.经BSSE校正后的C…F^-,C…Cl^-,C…Br^-和C…I^-体系分子识别相互作用能△E_CP分别为-314.0,-200.1,-183.3和-136.3 kJmol^-1,说明钳形受体C对F^-在热力学上具有最好的识别能力.此外,采用自然键轨道（NBO）)分析及分子中原子（AIM）等理论分析了C…X^-（X=F^-,Cl^-,Br^-和I^-）识别体系中红移氢键的电子结构和性质.     

茜素应用于识别硼酸的研究

应用紫外-可见分光光度法研究了茜素与硼酸之间的识别行为,结果表明,在pH 9.0Na2HPO4-NaH2PO4缓冲介质中,茜素与硼酸形成1∶1稳定络合物,使茜素的吸收光谱发生明显蓝移,溶液颜色由玫红色变为橙黄色,阴离子F-、Cl-、Br-、I-、Ac-、NO-3、C2O24-等均未引起茜素的吸收光谱及溶液颜色发生明显变化,因此茜素可以选择性识别硼酸。初步探讨了茜素与硼酸之间的相互作用机理,并对茜素识别硼酸与茜素识别阴离子的机理进行了比较。     

N-芳基-N′-(4-乙氧基苯甲酰基)硫脲衍生物阴离子识别性能的光谱研究

利用紫外-可见吸收光谱及1H NMR考察了两种N-芳基-N′-(4-乙氧基苯甲酰基)硫脲作为受体分子与F-,Cl-,Br-,I-,CH₃COO-,H₂PO-₄,HSO-₄,NO-₃等阴离子的作用。结果表明,客体阴离子F-,CH₃COO-,H₂PO-₄可以与该类受体分子形成氢键配合物,溶液颜色由无色转变为黄色,而加入其他阴离子则无变化。测定了主客体配合物的稳定常数和化学配位比,对苯环上不同取代基的受体分子与不同阴离子客体的识别作用以及同一受体对不同阴离子的识别作用进行了比较,其识别性能呈现规律性变化, 提出了可能的配合物的结合模式。     

HNO二聚体蓝移氢键的理论研究

利用分子轨道从头算理论和密度泛函理论结合不同理论基组对于N-H…O蓝移氢键进行了详细的研究.利用标准方法和均衡校正方法对二聚体进行了几何优化,振动频率和相互作用能的计算.拓扑学和自然键轨道理论对于蓝移氢键的本质进行分析.自然键轨道(NBO)分析表明,σ*(N-H)轨道上电子密度降低是电子密度重排效应的结果.分子内电子重排、轨道再杂化和电子受体内部结构重组共同作用结果导致了N-H的振动频率大幅蓝移现象的出现.     

N-邻羟基萘甲酰胺基-N′-苯基硫脲的合成及其对阴离子的识别

设计合成了3种N-邻羟基萘甲酰胺基-N′-苯基硫脲类化合物,通过核磁共振谱和质谱表征了其结构。应用吸收光谱和荧光光谱考察了在乙腈中其与F-、CH3CO2-、H2PO4-、HSO4-、Cl-和Br-等阴离子的相互作用。结果表明,该类主体分子与阴离子形成结合比为1∶1氢键配合物,通过改变萘环上酰基和羟基的相邻位置可调控识别作用的选择性,它们与阴离子作用分别在355、367nm和372nm出现最大吸收峰,荧光光谱显示它们对F-有突出的响应灵敏度,可选择性识别F-。     

2-F-环氧丁烷与几种生物小分子间的赝氢键结构

采用密度泛函B3LYP(Becke,three-parameter,Lee-Yang-PaH)/6-311++G**和HF(Hartree Fock)/6-311++G**方法,从理论上探讨了2-F-环氧丁烷分别与几种常见而重要的生物小分子咪唑(Iminazole)、噻唑(Thiazole)和恶唑(Oxazo1e)等分子间的弱相互作用,发现分子间同时存在N…H常规氢键和C-F…H-C赝氢键结构.弱相互作用能计算表明3个复合物的相对稳定性相当.计算结果表明,在C-F…H-C赝氢键结构中,与电子的直接供体F密切相关的共价键C-F键长增大,伸缩振动的频率红移,而作为电子受体的H-C基团,其C-H键伸缩振动光谱蓝移;另外,电子密度拓扑性质表明C-F…H-C赝氢键的共价性及离子性均与常规氢键相当.     

由四溴化碳、卤阴离子和溶剂分子组成的三角形卤键和氢键超分子复合物的理论与谱学研究

通过计算化学结合谱学实验揭示了四溴化碳与卤阴离子在质子溶剂中形成的CBr₄…X^-…H-C三角形的三键超分子复合物的作用模式. 卤键与氢键的强度均遵循：碘化物>溴化物>氯化物. 三键复合物中的卤键与氢键均呈现一定的协同效应. 紫外可见吸收光谱观察到四溴化碳与卤阴离子作用出现的新电荷转移峰,即卤键作用的吸收峰. 并利用Benesi-Hildebrand法确定了1:1的化学计量比、摩尔吸光系数及键合常数. 摩尔吸光系数及键合常数受溶剂的介电常数影响,在相同溶剂中遵循碘化物>溴化物>氯化物. 由键合常数表示的作用强度与理论计算的作用能相一致. 红外光谱测定的溶剂分子C-H振动频率随卤阴离子的加入有明显的红移,预示着C-H…X^-氢键的形成. 实验与理论均证明这种通过共享卤阴离子的三键复合物的存在.     

Abnormal synergistic effects between Lewis acid–base interaction and halogen bond in F3B···NCX···NCM

An abnormal synergistic effect was found between the Lewis acid–base interaction and halogen bond in triads F₃B···NCX···NCM (X and M are halogen atoms), where the strong Lewis acid–base interaction between F₃B and NCX has a larger enhancement than the weak halogen bond between NCX and NCM. This is in contrast with the traditional cooperative effect. It is interesting that the alkali-metal substituent as well as the heavier halogen atom play a more remarkable role in the enhancement of the interaction F₃B···NCX than that of NCX···NCM, particularly, the alkali-metal substituent makes the abnormal synergistic effect be the traditional cooperative one.     

C-H,C-N,C-O,N-N的键离解能和键长的计算

用B3LYP/6-311G**和CCSD/cc-pVDZ方法对CH4、CH3、CN、CO、N2、CH3NH2、CH3NO2、NH2NO2八个分子中的C-H、C-N、C-O、N-N键离解能进行计算,通过比较研究可知,计算CH3、CH3NH2、CH3NO2分子中的C-H键离解能和CN、CO、N2分子的键离解能用B3LYP/6-311G**方法可靠,而计算CH3-H、CH3-NH2、CH3-NO2和NH2-NO2分子的键离解能用CCSD/cc-pVDZ方法更可信;用以上二种方法对本文的八个分子的平衡几何结构进行优化求出所需的键长,通过比较可知,CH4、CH3、CN、CO、N2分子用B3LYP/6-311G**的方法进行平衡几何优化求得的键长更可靠,而CH3NO2、NH2NO2、CH3NH2分子则用CCSD/cc-pVDZ方法优化出的键长是更可信.     

Effects of a donor on the bond property of quantum-dot molecules

Within the framework of effective mass approximation, we have calculated the electronic structure of the two laterally coupled quantum dots with a donor by the finite element method. The calculated results show that the bond states of quantum-dot molecules are quite sensitive to the donor positions. By varying the donor position, the transition from covalent to ionic bond state is realized for some electronic states. Some extreme cases are also discussed for comparison.     

Comparison of hydrogen and halogen bonds between dimethyl sulfoxide and hypohalous acid: competition and cooperativity

A theoretical study of the complexes formed between dimethyl sulfoxide (DMSO) and hypohalous acid (HOX, X = Cl, Br, and I) has been carried out at the MP2/aug-cc-pVTZ level. For each HOX, four minima binary complexes were found, two mainly with an OH???O hydrogen bond and the other two with an OX???O halogen bond. The hydrogen-bonded complexes are more stable than the halogen-bonded analogues for HOCl and HOBr, while both types of complexes have similar stability in the iodine case. A red shift was found for the associated H–O and X–O bond stretch vibrations and a small blue shift for the distant bonds. As the oxygen of DMSO simultaneously binds with two HOCl molecules, the corresponding interactions are weakened with diminutive effect. This diminutive effect is the largest in the complexes with two OH???O hydrogen bonds but the smallest in those with two OCl???O halogen bonds.     

The study of the valence bond property in a two—different—quantum—dot molecule

The electronic energy spectrum and wavefunction of a quantum-dot molecule are studied by means of the finite-element solution of the single electron Schr?dinger equation. We find that the nature of the coupling can be covalent, ionic, or "intermediate" new mixed states, depending on various parameters such as the separation distance between two dots, the height of potential barrier, matching of the energies and parities of the orbital localized on each dot. The bond property can be used to explain the experimental result obtained by Oosterkamp et al. (1998 Nature 395 873).     

Symmetric bifurcated halogen bonds: substituent and cooperative effects

ABSTRACT

The aim of this study is to investigate the geometries, interaction energies and bonding properties of the symmetrical bifurcated halogen bond interactions (BXBs) by means of ab initio calculations. For this purpose, the NCX (X = Cl, Br) molecule is paired with a series of N-formyl formamide (NFF) derivatives (NFF-Z, Z = H, CN, CCH, OH, CH₃ and Li), and the properties of the resulting complexes are studied by molecular electrostatic potential, quantum theory of atoms in molecules, noncovalent interaction index and natural bond orbital analyses. For a fixed NCX molecule, interaction energies increase in the order of Z = Li > CH₃ > H > OH > CCH > CN. We found a strong correlation between the interaction energies of NCX:NFF-Z complexes and molecular electrostatic potential minimum values associated with NFF-Z monomers. Moreover, cooperative effects between BXB and X???N halogen bond interactions are studied in the ternary NCX:NCX:NFF-Z systems. Our results indicate that the strength of BXB interactions in the ternary complexes is enhanced by the presence of X???N bonds. Besides, cooperativity effects tend to increase the covalency of BXBs in these systems.     

Theoretical investigations of the hydrogen bond in a tetraamido/diamino quaternized macrocycle

ABSTRACT

We present theoretical investigations on the nature and persistence of the strong central hydrogen bond of a tetraamido/diamino quaternized macrocycle. Our theoretical study of the NMR properties of the central hydrogen bond proved difficult to reconcile with the available experimental results, suggesting the possibility of the non-persistence of the central hydrogen bond of the macrocycle in solution. We demonstrate alternative scenarios, in which a tautomerization of the macrocycle in solution gives rise to the experimentally observed NMR shifts.