高分子-无机夹层化合物的合成、结构和性能

由高分子和插入无机层状固体层间形成的夹层化合物是近年发展起来的一类具有诱人前景的新型功能材料,在许多领域具有广的前景。本文对这夹层化合的合成、结构、性能及应用前景等方面的研究进展进行了评述。     

多肽中氢键强度的理论研究

用B3LYP/6-31G^*法优化了多肽分子的几何构型,计算了各个构型的电荷分布和氢键酸度,进而对多肽分子中的氢键强度进行了研究.结果表明,多肽分子中氢键的强度同时取决于形成氢键的H…O原子间距R和N-H…O之间的键角β;多肽分子倾向于形成R值小、β值大的大环氢键.3₁₀螺旋结构的多肽分子中的氢键具有协同效应,分子越大,分子中氢键越多,氢键的协同效应越强.     

氢键给体和受体对纤维素醚复合薄膜后处理的影响研究

纤维素醚是一类水溶性大分子,它可以作为氢键受体和聚丙烯酸(PAA)形成氢键复合物。利用层层组装的方法制备出羟乙基纤维素(HEC)与PAA的界面复合薄膜,选取氢键给体单宁酸(TA)和氢键受体甲基纤维素(MC)、羟丙基纤维素(HPC)、聚乙烯吡咯烷酮(PVPON)溶液分别对薄膜进行浸泡后处理。研究表明浸泡后处理是一个动态的过程,会改变薄膜的厚度和组成,对于薄膜的实际应用具有指导意义,为多组分复合薄膜的制备提供了新思路。     

分子内氢键对化合物性质的影响

本文从几个方面介绍了分子内氢键对有机化合物性质的影响。     

由氢键构筑的两个超分子化合物的合成与结构

本文通过质子化内消旋大环配体[meso-H2L]^2＋及其外消旋镍配合物[Ni（rac-L）]^2＋与金属氧酸离子（[VO3]^-/[CrO4]^2）在水溶液中进行超分子组装得到两个氢键连接的超分子化合物[Ni（rac-L）]3[CrO4]2[ClO4]2·4H2O（1）和[meso-H2L][VO3]2·0.33H2O（2）.通过IR、元素分析、X-ray单晶衍射、热重等对其结构进行了表征.化合物1由[Ni（rac-L）]^2＋与CrO4^2-和水分子通过大环中的胺分子与CrO4^2-和水分子形成的氢键组成一维六方棱柱状结构.化合物2则由[VO3]n^n-阴离子螺旋链通过分子间氢键连接[meso-H2L]^2＋构成具有一维疏水通道的三维超分子化合物.研究结果表明氢键在超分子组装中起着重要的作用.     

氢键的量子化学研究(Ⅰ) 氢键类型和强度的量子化学指标

X和HY形成的氢键体系XHY,可能存在着共价形氢键X_…H-Y或离子型氢键[X-H]_…~+Y~-.区分这两种电荷的分布,量子化学计算尚有不确切之处,且对于分子内氢键的情况,无法划分XH和Y.此外,对于共价型氢键复合物还有一个稳定性问题也需要用适当的量子化学方法来衡量.     

煤中氢键类型的研究煤中氢键类型的研究

采用真空红外光谱技术清晰地观察到了碳含量７３～８８ｗ％（ｄａｆ）的四个煤样及其溶剂抽出物中的五种羟基的不同氢键缔合类型，并通过原位热解红外光谱技术研究了它们的热稳定性。结果表明，它们的热稳定性顺序为：ＯＨ…π＜ＯＨ…Ｎ＜ＯＨ自缔合≈环状四聚体ＯＨ＜ＯＨ…醚氧。     

固体NMR研究PAA/PEO共混物中氢键相互作用与结构演化

分子间相互作用是决定材料结构和性能的关键因素之一,而如何在分子水上实现对复杂相互作用分子的检测仍然是一个挑战性课题。本工作首先在不同p H值条下以聚丙烯酸/聚环氧乙烷(PAA/PEO)的混合水溶液制备了系列的固体薄膜,然后采用多种基于连续相调制多脉冲技术的一维和二维~1H多脉冲去耦(CRAMPS)固体NMR新技术,并结合高分辨~(13)C交叉极化魔角旋转(CPMAS)、~(23)Na多量子(MQ)等多核固体NMR实验,对PAA/PEO聚合物共混物的微观结构和动力学进行了原位和系统的研究。通过不同类型的~1H高分辨CRAMPS实验检测到共混物中包含多种不同类型质子:通过氢键相互作用形成二聚体的COOH基团、自由COOH基团、与水结合的COOH基团和主链基团。随着p H值的升高,除主链质子外,大部分其它区域的信号都明显降低,这是由于PAA与PEO以及水的氢键作用减弱所致。这些CRAMPS NMR技术也被用来阐明不同p H值制备的样品中不同基团的分子运动性。此外,二维~1H-~1H自旋交换NMR实验提供了关于聚合物PAA与PEO大分子链间、以及水与聚合物的相互作用。~1H自旋扩散实验表明,在这些共混物中明显存在相微观相分离的结构,并且测定的分散相区尺寸约为17 nm。~(23)Na MQMAS实验揭示了在共混物中存在两种类型~(23)Na位,一种是自由的钠离子,另一种是与大分子相互作用的Na离子。特别是通过~1H-检测的~(23)Na-~1H CPMAS实验揭示了Na~+离子的位置远离PEO而与PAA临近。上述这些SSNMR实验结果在分子水平上提供了氢键相互作用对PAA/PEO共混物微观结构和动力学影响的详细信息,可以获得不同p H值对PAA与PEO的氢键作用、相容性、微观结构、水-聚合物相互作用和不同组分分子运动性的影响。在上述核磁共振研究的基础上,我们提出了一种新的PAA/PEO共混物的结构模型,该模型首次成功地揭示了不同的p H值对PAA/PEO共混物中微观结构和动力学的影响。本工作清楚地表明,固态核磁共振是在分子水平上研究具有复杂相互作用的多相聚合物材料的有力工具。本文的研究工作对于探索检测聚合物弱相互作用的新方法和发展基于氢键相互作用的聚合物新材料的开发具有重要意义。     

尿素及硫脲与羰基化合物间的氢键相互作用

利用量子化学二级微扰理论方法对尿素及硫脲衍生物与羰基化合物之间的氢键复合物进行了研究, 在自然键轨道分析基础上进一步揭示了氢键本质并研究了取代基效应. 结果表明, 羰基化合物中供电子基和共轭基, 尿素及硫脲中的吸电子基和共轭基均有利于氢键的形成. 结合尿素与硫脲的催化反应过程, 讨论了氢键复合物两种可能的顺反异构并分析比较了顺反式构象异构体的稳定能大小.     

给受体型化合物电氧化还原的电子结构

用MNDO方法研究了氰基乙烯基苯胺衍生物的电氧化还原行为, 以及给受体的前线轨道作用. 它们的共同氧化峰是给体氨基氮原子失去一个电子, 共同的还原峰是受体乙烯基反键轨道得到一个电子. 甲基的空间效应使DCEDMA形成准可逆的单电子过程. 稳定的叔自由基使TCEA~(-·)得到一个电子但又可失去.     

The Balance between Hydrogen Bonds,Halogen Bonds,and Chalcogen Bonds in the Crystal Structures of a Series of 1,3,4-Chalcogenadiazoles

In order to explore how specific atom-to-atom replacements change the electrostatic potentials on 1,3,4-chalcogenadiazole derivatives, and to deliberately alter the balance between intermolecular interactions, four target molecules were synthesized and characterized. DFT calculations indicated that the atom-to-atom substitution of Br with I, and S with Se enhanced the σ-hole potentials, thus increasing the structure directing ability of halogen bonds and chalcogen bonds as compared to intermolecular hydrogen bonding. The delicate balance between these intermolecular forces was further underlined by the formation of two polymorphs of 5-(4-iodophenyl)-1,3,4-thiadiazol-2-amine; Form I displayed all three interactions while Form II only showed hydrogen and chalcogen bonding. The results emphasize that the deliberate alterations of the electrostatic potential on polarizable atoms can cause specific and deliberate changes to the main synthons and subsequent assemblies in the structures of this family of compounds.     

On the Relationship between Hydrogen Bond Strength and the Formation Energy in Resonance-Assisted Hydrogen Bonds

Resonance-assisted hydrogen bonds (RAHB) are intramolecular contacts that are characterised by being particularly energetic. This fact is often attributed to the delocalisation of π electrons in the system. In the present article, we assess this thesis via the examination of the effect of electron-withdrawing and electron-donating groups, namely −F, −Cl, −Br, −CF₃, −N(CH₃)₂, −OCH₃, −NHCOCH₃ on the strength of the RAHB in malondialdehyde by using the Quantum Theory of Atoms in Molecules (QTAIM) and the Interacting Quantum Atoms (IQA) analyses. We show that the influence of the investigated substituents on the strength of the investigated RAHBs depends largely on its position within the π skeleton. We also examine the relationship between the formation energy of the RAHB and the hydrogen bond interaction energy as defined by the IQA method of wave function analysis. We demonstrate that these substituents can have different effects on the formation and interaction energies, casting doubts regarding the use of different parameters as indicators of the RAHB formation energies. Finally, we also demonstrate how the energy density can offer an estimation of the IQA interaction energy, and therefore of the HB strength, at a reduced computational cost for these important interactions. We expected that the results reported herein will provide a valuable understanding in the assessment of the energetics of RAHB and other intramolecular interactions.     

Mutual Weakening of Hydrogen Bonds Between Hydrogen Fluoride and Proton Donors

The mutual effect of hydrogen bonds in BHF(HHal) _n complexes (Hal = F, Cl, Br, I; B = –, CH₃CN, NH₃; n = 1-3) was examined using the self-consistent field ab initio approach (6-31++G(d,p) and ECP-HW). When two and three equivalent H bonds are formed from the lone electron pairs of the fluorine atom of the HF molecule, the mutual weakening effect is 17% and 28%, respectively. The coefficients of the mutual effects of hydrogen bonds in HF(HHal)₂ and H₂O(HHal)₂ bridges are close in magnitude.     

Synthesis of Metastable Inorganic Solids with Extended Structures

The number of known inorganic compounds is dramatically less than predicted due to synthetic challenges, which often constrains products to only the thermodynamically most stable compounds. Consequently, a mechanism-based approach to inorganic solids with designed structures is the holy grail of solid state synthesis. This article discusses a number of synthetic approaches using the concept of an energy landscape, which describes the complex relationship between the energy of different atomic configurations as a function of a variety of parameters such as initial structure, temperature, pressure, and composition. Nucleation limited synthesis approaches with high diffusion rates are contrasted with diffusion limited synthesis approaches. One challenge to the synthesis of new compounds is the inability to accurately predict what structures might be local free energy minima in the free energy landscape. Approaches to this challenge include predicting potentially stable compounds thorough the use of structural homologies and/or theoretical calculations. A second challenge to the synthesis of metastable inorganic solids is developing approaches to move across the energy landscape to a desired local free energy minimum while avoiding deeper free energy minima, such as stable binary compounds, as reaction intermediates. An approach using amorphous intermediates is presented, where local composition can be used to prepare metastable compounds. Designed nanoarchitecture built into a precursor can be preserved at low reaction temperatures and used to direct the reaction to specific structural homologs.     

Strength of Intramolecular Hydrogen Bonds

The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.     

Intramolecular Resonance-assisted Hydrogen Bonds in N-Salicylidene-anilines

In the crystal structures of N-salicylidene-anilines, the ortho-OH group with the central N atom forms a planar six-membered ring through intramolecular hydrogen bonds (Fig. 1). The pseudo-aromatic ring is coplanar with its attached phenyl ring. The resonance strengthens the H-bond through proton transfer between the O and N atoms (Fig.1,Ⅰ←→Ⅱ): dco and dcc become shorter and dCN longer significantly. The d1～d6 are also changed regularly. According to the geometries obtained from X-ray analysis and retrieved from the Cambridge Structural Database (CSD, version 5.21), we believe that the main resonance, at least in solid state, is the molecular keto form (Ⅱ, Fig. 1) instead of the zwitterionic one (Ⅲ, Fig.1).     

Lewis Acid Transition-Metal-Catalyzed Hydrogen Activation: Structures,Mechanisms, and Reactivities

As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H₂ activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ⁴-L₃B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ³-L₂B-Co complex bis-phosphino-boryl (PBP)-Co, the η²-BC-type κ³-L₂B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ²-LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments.     

Hydrogen and Halogen Bonding in Homogeneous External Electric Fields: Modulating the Bond Strengths

Recent years have witnessed various fascinating phenomena arising from the interactions of noncovalent bonds with homogeneous external electric fields (EEFs). Here we performed a computational study to interpret the sensitivity of intrinsic bond strengths to EEFs in terms of steric effect and orbital interactions. The block-localized wavefunction (BLW) method, which combines the advantages of both ab initio valence bond (VB) theory and molecular orbital (MO) theory, and the subsequent energy decomposition (BLW-ED) approach were adopted. The sensitivity was monitored and analyzed using the induced energy term, which is the variation in each energy component along the EEF strength. Systems with single or multiple hydrogen (H) or halogen (X) bond(s) were also examined. It was found that the X-bond strength change to EEFs mainly stems from the covalency change, while generally the steric effect rules the response of H-bonds to EEFs. Furthermore, X-bonds are more sensitive to EEFs, with the key difference between H- and X-bonds lying in the charge transfer interaction. Since phenylboronic acid has been experimentally used as a smart linker in EEFs, switchable sensitivity was scrutinized with the example of the phenylboronic acid dimer, which exhibits two conformations with either antiparallel or parallel H-bonds, thereby, opposite or consistent responses to EEFs. Among the studied systems, the quadruple X-bonds in molecular capsules exhibit remarkable sensitivity, with its interaction energy increased by −95.2 kJ mol⁻¹ at the EEF strength 0.005 a.u.     

Crystal Structures and Packing of 4-Cyanocubanecarboxylic Acid,Its Methyl Ester,and the Solid Solution of 1,4-Dicyanocubane and 1,4-Dibromocubane

The crystal structure of 4-cyanocubanecarboxylic acid contains the same syn–anti carboxyl group catemer that is found in other cubane monocarboxylic acids. The cyano groups are arranged according to the type-II geometry, in that they are 2₁ screw-axis related. Curiously, there is a 5% orientational disorder of the cyano and anti carboxyl groups. The ester of the title acid packs isostructurally with the corresponding chloro and fluoro analogs because of the importance of the C—H...O hydrogen bond patterns. 1,4-Dicyanocubane forms solid solutions with 1,4-dibromocubane, but, interestingly, the crystal structure of the solid solution is distinct from that of either component. The formation of these solid solutions seems to be governed by shape and size factors.     

Synthesis, Characterization and Fluorescence of a One-dimensional Cadmium( Ⅱ ) Compound Involving Covalent and Hydrogen Bonds

The title compound [Cd(Hq)2(Hdpa)2] (Hq = 8-hydroxyquinoline, H2dpa = diphenic acid) has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group C2/c with a = 20.6880(5), b = 14.2584(4), c = 13.4776(4) (A), β = 113.434(2)°, C46H28Cd1N2O10, Mr = 881.10, V = 3647.68(17) (A)3, Z = 4, Dc = 1.604 g/cm3, F(000) = 1784,μ = 0.668 mm-1, the final R = 0.0576 and wR = 0.1157 for 2631 observed reflections with I ＞2σ(Ⅰ). The centrosymmetric Cd(Ⅱ) ion is six-coordinated in a slightly distorted octahedral geometry.The intermolecular hydrogen bonds extend the mononuclear structure into a one-dimensional supramolecular framework. The fluorescence spectrum of the compound exhibits intense emission at 520 nm when excited at 330 nm in solid state at room temperature.