质子受体取代基对苯甲酸-吡啶中O-H…N氢键强度的影响

氢键在材料科学、化学等方面具有重要的作用。对氢键的强度和本质进行深入的研究具有重要的意义。Zheng等对苯甲酸-吡啶的超分子液晶合成进行了研究,通过改变苯甲酸的结构,对超分子液晶的结构和性质进行了研究。以吡啶作为质子受体分子,苯甲酸作为质子供体分子,不同取代基对O-H…N氢键强度的影响。     

氢键诱导超分子液晶化合物的合成及表征

两个超分子液晶化合物--苯乙烯基吡啶氢键型液晶通过以4-羟基-4′-苯乙烯基吡啶及其末端含有双键的衍生物为质子受体,以4-戊氧基苯甲酸为质子供体,四氢呋喃为溶剂而合成.用IR、1HNMR和元素分析对所合成的化合物进行了结构表征,并用DSC和带热台的偏光显微镜分别对质子供体和超分子复合物复合前后的液晶行为进行了研究.结果表明:合成了目标化合物;IR结果证明了羧基和吡啶环间分子间氢键代替了羧基间的分子间氢键,复合物表现出分子的热力学行为;液晶行为研究证明了氢键复合物是典型的热致液晶且呈现明显的向列型液晶态,超分子液晶复合物较质子供体的液晶相范围宽且其相转变温度低于质子供体,说明分子间氢键起到了稳定液晶相态的作用.     

超分子聚氨酯的合成及应用研究进展

综述了超分子聚氨酯的合成方法,利用氢键相互作用、电子供体-受体相互作用、离子相互作用等分子间非共价键的键合作用而制得超分子聚氨酯,并介绍了超分子聚氨酯主要在液晶材料、涂层材料、形状记忆材料的应用。     

氢键液晶分子结构与性能研究

结合氢键和液晶的特异性能，对氢键自愈的弹性体液晶、氢键自组装的超分子液晶体系、氢键液晶模型理论进行了对比研究。同时，指出了氢键液晶研究中所面临的挑战，分析了氢键液晶的动态可逆性、响应性、自适应性以及粗粒化模型理论的优点。     

弱分子间力超分子液晶性能的分析

超分子液晶是利用氢键、离子相互作用、电荷转移相互作用、疏水相互作用及范德华力等弱分子间相互作用构筑的多种超分子液晶复合体系。超分子液晶复合体系具有质量或电荷传输性、传递性、信息储存功能、分子传感等动态功能性、环境友好性及低能耗加工性等特点。对超分子液晶的性能影响因素进行了深入分析与研究,并对超分子液晶分类进行了介绍。     

分子间自组装盘状液晶材料研究进展

综述了近十年来国内外报道的分子间自组装盘状液晶的研究进展;重点阐述了通过分子间氢键或金属离子配位键自组装的盘状液晶小分子和超分子液晶的液晶性能、掺杂了无机纳米粒子的通过氢键形成的液晶材料的光电性能及其在有机光伏器件中的应用;最后总结了不同类分子间自组装盘状液晶的性能优势。综合文献报道可知,引入分子间氢键或配位键可以更好地实现盘状液晶在特定功能材料中的应用,并且自组装的盘状液晶还可与纳米粒子形成复合物,得到具有特定功能的纳米复合材料。     

基于弱分子间力超分子液晶性能影响因素分析（下）

超分子液晶是利用氢键、离子相互作用;电荷转移相互作用;疏水相互作用及范德华力等弱分子间相互作用构筑的多种超分子液晶复合体系。这种弱分子间力具有动态可逆性,对外部环境（压力、温度、磁场、电场、pH值、光感、化学反应等）具有通过氢键的缔合与解缔合以及电荷转移来改变其结构的独特的响应刺激的功能特性。另外,利用弱分子间力构筑的超分子液晶复合体系具有质量或电荷传输性、传递性、信息储存功能、分子传感等动态功能性、环境友好性及低能耗加工性等特点,故该领域将是未来材料科学体系发展的主方向。对超分子液晶性能影响因素进行了深入分析与研究,并对超分子液晶分类作了介绍。     

基于弱分子间力超分子液晶性能影响因素分析（上）

超分子液晶是利用氢键、离子相互作用;电荷转移相互作用;疏水相互作用及范德华力等弱分子间相互作用构筑的多种超分子液晶复合体系。这种弱分子间力具有动态可逆性,对外部环境（压力、温度、磁场、电场、pH值、光感、化学反应等）具有通过氢键的缔合与解缔合以及电荷转移来改变其结构的独特的响应刺激的功能特性。另外,利用弱分子间力构筑的超分子液晶复合体系具有质量或电荷传输性、传递性、信息储存功能、分子传感等动态功能性、环境友好性及低能耗加工性等特点,故该领域将是未来材料科学体系发展的主方向。对超分子液晶性能影响因素进行了深入分析与研究,并对超分子液晶分类进行了介绍。     

基于弱分子间力超分子液晶性能影响因素分析

超分子液晶是利用氢键、离子相互作用、电荷转移相互作用、疏水相互作用及范德华力等弱分子间相互作用构筑的多种超分子液晶复合体系.这种弱分子间力具有动态可逆性,对外部环境(压力、温度、磁场、电场、pH值、光感、化学反应等)具有通过氢键的缔合与解缔合以及电荷转移来改变其结构的独特的响应刺激的功能特性.另外,利用弱分子间力构筑的超分子液晶复合体系具有质量或电荷传输性、传递性、信息储存功能、分子传感等动态功能性、环境友好性及低能耗加工性等特点,故该领域将是未来材料科学体系发展的主方向.本文对超分子液晶的性能影响因素进行了深入分析与研究,并对超分子液晶分类进行了介绍.     

含超分子液晶结构的PA液晶与PA共混物的制备方法

一种含超分子液晶结构的PA液晶与PA共混物的制备方法，属于PA共混物液晶化自增强工程塑料领域。由于刚性分子与柔性分子聚合物的结构差异较大，二者很难形成分子级别相容的共混物。本发明首先合成PA液晶，然后利用溶液共混的方法，通过PA液晶和PA之间强烈的分子间氢键作用，将物质的量比为1：1的PA液晶与PA自组装合成了具有超分子液晶的共混物。     

Hydrogen Bonding Modules for Use in Supramolecular Polymers

Supramolecular polymer chemistry has emerged as a major research focus within polymer science, because of the potential to improve material properties, through the combination of noncovalent interactions and synthetic polymers. As a supramolecular handle, the most useful noncovalent interaction is hydrogen bonding, which has been used extensively, because of advantages such as synthetic accessibility, directionality, fidelity, and, most importantly, responsiveness to external stimuli. This review introduces recent advances in the development of hydrogen bonding modules that can be useful for creating a variety of supramolecular polymers. Furthermore, we present selected examples of hydrogen bonded supramolecular polymers from the literature, by dividing them into three categories: supramolecular polymers assembled from small molecules, and main-chain and side-chain supramolecular polymers.     

A thermosensitive supramolecular aggregation from linear telechelic polydimethylsiloxane with self-assembly units

A new thermosensitive material, polydimethylsiloxane supramolecular aggregation (PDMS-SMA-1), was prepared by coupling the N-pyridin-2-yl-succinamic acid with aminopropyl-terminated polydimethylsiloxane via amidated reaction. Its structure was confirmed by FT-IR, ¹H NMR and ¹³C NMR. And the FT-IR spectra, molecular dynamics simulations and density functional theory calculations supported the existence of intermolecular hydrogen bonding and π-π stacking in supramolecular aggregation and obtained its possible self-assembly structure. A combination of DSC measurements, oscillatory shear experiments, and AFM measurements was carried out to further investigate the nature of PDMS-SMA-1. The results indicated that hydrogen bonding and π-π stacking combined with phase segregation were important for the preparation of thermosensitive materials. Moreover, in order to investigate the effect of molecular weight on the thermal sensitivity and morphology of supramolecular aggregation, PDMS-SMA-2 with higher molecular weight was also synthesized. In contrast to PDMS-SMA-1, it had similar thermal properties but different morphology. All the characteristics of supramolecular aggregation suggested a much wider range of hydrogen bonding and π-π stacking motifs which could be applied in intelligent materials.     

Self-Healable,Highly Stretchable Modified Epoxy Resin Materials by Incorporation with Quadruple Hydrogen-Bonded Supramolecular Polymers

Among the multiple hydrogen bonding compounds, 2-ureido-4[1H]-6-methyl-pyrimidinone (UPy) derivatives are most used for fabrication of functional supramolecular assemblies based on the strong quadruple hydrogen bonding between UPy moieties. In this work, a self-healable and highly stretchable epoxy resin system with high heal efficiency is designed and prepared by the composite of UPy-modified epoxy resin and UPy-terminated supramolecular polymers. The elongation at break of the highly stretchable epoxy resin reaches 247% and the tensile strength of the material is 3.10 MPa with tensile test. The mechanical properties of the material (which is cut into two parts) can be restored to 99% (the elongation at break is 246% and the tensile strength is 2.80 MPa) after 2 h of heating at 90 °C. As a bulk material, the supramolecular polymer incorporated epoxy resin could maintain its mechanical properties when used as a healable substrate for conductive experiments. This line of research may provide a new approach for design and preparation of novel self-healable epoxy resin materials.     

Halogen bonds in 2D supramolecular self-assembly of organic semiconductors

Weak interactions between bromine, sulphur, and hydrogen are shown to stabilize 2D supramolecular monolayers at the liquid-solid interface. Three different thiophene-based semiconducting organic molecules assemble into close-packed ultrathin ordered layers. A combination of scanning tunneling microscopy (STM) and density functional theory (DFT) elucidates the interactions within the monolayer. Electrostatic interactions are identified as the driving force for intermolecular BrBr and BrH bonding. We find that the SS interactions of the 2D supramolecular layers correlate with the hole mobilities of thin film transistors of the same materials.     

Hydrogen bond‐mediated self‐assembly and supramolecular structures of diblock copolymer mixtures

This review summarizes recent advances in the preparation of hydrogen bonding block copolymer mixtures and the supramolecular structures they form through multiple hydrogen bonding interactions. Hydrogen bonding in block copolymer mixtures that form nanostructures and have unusual electronic, photonic and magnetic properties is a topic of great interest in polymer science. Combining the self‐assembly of block copolymers with supramolecular structures offers unique possibilities to create new materials with tunable and responsive properties. The self‐assembly of structures from diblock copolymer mixtures in the bulk state is readily controlled by varying the weight fraction of the block copolymer mixture and the copolymer composition; in solution, the morphologies are dependent on the copolymer composition, the copolymer concentration, the nature of the common solvent, the amount of the selective solvent and, most importantly, the hydrogen bonding strength. Copyright © 2008 Society of Chemical Industry     

基于超分子化学方法制备自愈合聚合物材料的研究进展

本文综述了超分子化学方法制备自愈合聚合物材料的研究进展,着重介绍了利用氢键、π-π键、离子键等非共价键主-客体相互作用来制备自愈合聚合物材料的研究现状。     

Halogen bonding based recognition processes: a world parallel to hydrogen bonding

Halogen bonding is the noncovalent interaction between halogen atoms (Lewis acids) and neutral or anionic Lewis bases. The main features of the interaction are given, and the close similarity with the hydrogen bonding will become apparent. Some heuristic principles are presented to develop a rational crystal engineering based on halogen bonding. The focus is on halogen-bonded supramolecular architectures given by halocarbons. The potential of the interaction is shown by useful applications in the field of synthetic chemistry, material science, and bioorganic chemistry.     

Perspectives on main‐chain hydrogen bonded supramolecular polymers

Supramolecular polymers are assembled from monomeric units held together by reversible non‐covalent interactions. These supramolecular materials display polymeric properties and may soon have important industrial applications. This mini review focuses on the advances in main‐chain supramolecular polymers whose assembly is guided primarily by hydrogen bonding interactions. The design constraints of these new systems discussed include assembly motifs, the strength and directionality of the non‐covalent interactions, association versus reversibility, and environmental effects on the degree of polymerization. Selected literature examples including Meijer's ureidopyrimidinone system are used to highlight the challenges and potential of these supramolecular polymeric materials. Copyright © 2007 Society of Chemical Industry     

Heat Shrinkable Behaviour of Supramolecular Hydrogen Bonded Maleated Ethylene Propylene Diene Rubber and Maleated High Density Polyethylene Blend

Maleated high density polyethylene and maleated ethylene propylene diene rubber (50 wt%/50 wt%) was blended in presense of 3-amino-1,2,4-triazole (ATA). The supramolecular hydrogen bonding was characterized by FTIR and dynamic mechanical analysis. The crystallinity of the blend system was studied by XRD and it was observed that supramolecular hydrogen bonding decreases the crystallinity of the blend. The supramolecular hydrogen bonded network improves heat shrinkability of the blend.     

Exploring the complexity of supramolecular interactions for patterning at the liquid-solid interface

The use of self-assembly to fabricate surface-confined adsorbed layers (adlayers) from molecular components provides a simple means of producing complex functional surfaces. The molecular self-assembly process relies on supramolecular interactions sustained by noncovalent forces such as van der Waals, electrostatic, dipole-dipole, and hydrogen bonding interactions. Researchers have exploited these noncovalent bonding motifs to construct well-defined two-dimensional (2D) architectures at the liquid-solid interface. Despite myriad examples of 2D molecular assembly, most of these early findings were serendipitous because the intermolecular interactions involved in the process are often numerous, subtle, cooperative, and multifaceted. As a consequence, the ability to tailor supramolecular patterns has evolved slowly. Insight gained from various studies over the years has contributed significantly to the knowledge of supramolecular interactions, and the stage is now set to systematically engineer the 2D supramolecular networks in a "preprogrammed" fashion. The control over 2D self-assembly of molecules has many important implications. Through appropriate manipulation of supramolecular interactions, one can "encode" the information at the molecular level via structural features such as functional groups, substitution patterns, and chiral centers which could then be retrieved, transferred, or amplified at the supramolecular level through well-defined molecular recognition processes. This ability allows for precise control over the nanoscale structure and function of patterned surfaces. A clearer understanding and effective use of these interactions could lead to the development of functional surfaces with potential applications in molecular electronics, chiral separations, sensors based on host-guest systems, and thin film materials for lubrication. In this Account, we portray our various attempts to achieve rational design of self-assembled adlayers by exploiting the aforementioned complex interactions at the liquid-solid interface. The liquid-solid interface presents a unique medium to construct flawless networks of surface confined molecules. The presence of substrate and solvent provides an additional handle for steering the self-assembly of molecules. Scanning tunneling microscopy (STM) was used for probing these molecular layers, a technique that serves not only as a visualization tool but could also be employed for active manipulation of molecules. The supramolecular systems described here are only weakly adsorbed on a substrate, which is typically highly oriented pyrolytic graphite (HOPG). Starting with fundamental studies of substrate and solvent influence on molecular self-assembly, this Account describes progressively complex aspects such as multicomponent self-assembly via 2D crystal engineering, emergence, and induction of chirality and stimulus responsive supramolecular systems.