从超分子聚合物到超分子有机框架:组装溶液相超分子结构的周期性

单体分子在溶液相自发形成周期性的网络结构,是超分子化学和分子自组装研究领域的重大挑战.多头基分子在溶液相通过分子间非共价键作用可以形成超分子聚合物.提高多头基(三头基和四头基)分子骨架的刚性,可以提高结合位点的结构预组织,进而增强分子间相互作用的协同性和多价性特征,提高自组装结构的有序性或周期性.本文综述了多头基分子自组装形成超分子聚合物的一些重要进展,介绍了二维超分子有机框架(一类新的溶液相周期性自组装网络结构研究的最新进展.     

Two-Dimensional Covalent and Supramolecular Polymers: From Monolayer to Bilayer and the Thicker

Selective preparation of two-dimensional polymers (2DPs) and supramolecular polymers (2DSPs) with defined thickness is crucially important for controlling and maximizing their functions, yet it has remained as a synthetic challenge. In the past decade, several approaches have been developed to allow selective preparation of discrete monolayer 2DPs and 2DSPs. Recently, crystal exfoliation and self-assembly strategies have been employed to successfully prepare bilayer 2DP and 2DSP, which represent the first step towards the controlled “growth” of 2D polymers from the thinnest monolayers to thicker few-layers along the third dimension. This Concept review discusses the concept of accurate synthesis of 2D polymers with defined layers. Advances in this research area will pave the way to rational synthetic strategies for 2D polymers with controlled thickness.     

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

We introduce monosaccharides as versatile water‐soluble units to compatibilise supramolecular polymers based on the benzene‐1,3,5‐tricarboxamide (BTA) moiety with water. A library of monosaccharide‐based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α‐glucose, β‐glucose, α‐mannose and α‐galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one‐dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self‐assembly process is operative and that the introduction of different monosaccharides does not significantly change the self‐ assembly behaviour. Finally, we investigate the potential of post‐assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy.     

Photo‐Powered Collapse of Supramolecular Polymers Based on an Overcrowded Alkene Switch

A supramolecular polymer was constructed from a light‐driven overcrowded alkene switch modified with two alkylated gallic acid amide pendants ( MSP‐1 ). Upon UV irradiation, stable MSP‐1 isomerized into unstable MSP‐2 , which induced the effective collapse of well‐defined cross‐linked supramolecular polymers, and the reassembly can be realized by aging at low temperature.     

Aromatic Embrace Motifs for Bulk Supramolecular Polymers

Frequently encountered in crystalline materials, aromatic embraces (AEs) are formed when arylated molecules interact through multiple concerted aromatic interactions. AEs are a robust motif that is suitable for the preparation of amorphous bulk supramolecular polymers (BSPs). Crystal engineering revealed that the polymorphic compound (PPh₃)(Cp)Fe(CO){CO(CH₂)₅CH₃} (Cp=cyclopentadienyl), known as FpC₆, assembled into various chain structures through several AE motifs. Upon melting, FpC₆ always adopted the same AE motif, which extended into the corresponding embracing “ladder” chains. The resultant BSP displayed typical polymer behaviour, including the presence of a glass transition and viscoelasticity, which allowed the effect of thermal history on the polymerisation behaviour to be explored. The ladder chains formed by the AE remain assembled at temperatures of up to 130 °C and were able to effectively suppress crystallisation during cooling. The ability of the AE to form chains at high temperatures and suppress crystallisation is a new opportunity to advance the field of BSPs and supramolecular chemistry.     

基于β-环糊精和二茂铁主客体作用的超分子聚合物的制备及其凝胶化

以β-环糊精修饰的壳聚糖（CDCS）和二茂铁修饰的聚乙二醇（FCPEG）为构筑单元,以伊环糊精和二茂铁的主客体相互作用为驱动,构筑了水溶性的超分子聚合物CDCS-FCPEG。在此基础上,加入α-环糊精（α-CD）,通过其对聚乙二醇的穿环络合诱导结晶作用,制备了壳聚糖基水凝胶。使用核磁（^1H—NMR）、紫外一可见光谱法（UV—Vis）、X射线衍射分析（XRD）和循环伏安法（CV）等手段进行了验证。结果表明：超分子聚合物CDCS—FCPEG与共价键连接的传统聚合物一样可以和α—CD形成凝胶。     

氢键识别超分子聚合物的新进展

近年来,由于氢键作用对聚合物的热力学性质、微观自组装、结晶及液晶行为的重要影响,氢键识别在超分子聚合物的分子设计与结构控制方面的应用受到广泛关注。本文系统介绍了氢键识别体系的类型与性质,以及分子结构、分子内氢键对氢键识别强度的影响,讨论了羧酸与吡啶间氢键识别体系、与核苷相关的氢键识别体系以及四重氢键识别体系在超分子聚合物中的最新应用,主要介绍了氢键识别超分子聚合物的合成、结构、性质及功能。     

Deep Eutectic Supramolecular Polymers: Bulk Supramolecular Materials

Application of new strategies for supramolecular self‐assembly can significantly impact the properties and/or functions of supramolecular polymers. To realize a facial strategy for the development of solvent‐free supramolecular polymers in bulk, “deep eutectic solvents” were employed. Cyclodextrins and natural acids were used to prepare deep eutectic supramolecular polymers ( DESP s). Deep eutectic solvents have special characteristics that endow DESP s with unique macroscopic properties and excellent processability. DESP s exhibit supramolecular adhesion and temperature‐dependent behavior originating from the combined effects of deep eutectic solvents and supramolecular polymerization. Because DESP s are solvent‐free and display interesting macroscopic properties, they have potential as new adaptive materials.     

Urea Derivatives as Functional Molecules: Supramolecular Capsules,Supramolecular Polymers,Supramolecular Gels,Artificial Hosts,and Catalysts

Urea, which has both hydrogen bond acceptor and donor moieties, is an ideal structure for a supramolecular synthon. Various supramolecules having ureido group(s) have been widely developed. This article summarizes recent developments of urea derivatives that exhibit various functions: i) supramolecular capsules that form discrete urea–urea intermolecular hydrogen bonds, ii) supramolecular polymers that form continuous urea–urea intermolecular hydrogen bonds, iii) supramolecular gels that form continuous urea–urea intermolecular hydrogen bonds, iv) artificial host molecules based on the molecular recognition ability of the ureido group, and v) catalytic reactions developed by utilizing the molecular recognition ability of the ureido group.     

Hierarchy of Asymmetry in Chiral Supramolecular Polymers: Toward Functional,Helical Supramolecular Structures

The formation of helical structures through the supramolecular polymerization of a variety of self-assembling units is reviewed. These scaffolds are usually obtained by efficient transfer or amplification of chirality phenomena, in which the starting self-assembling molecules possess different elements of asymmetry, such as point or axial chirality. Relevant examples of helical supramolecular structures investigated under thermodynamic control are reviewed, and the helical outcome of remarkable examples of chiral entities obtained through kinetic control are also highlighted. Finally, selected examples of flexible macroscopic chirality and catalysis are described to illustrate the applicability of helical aggregates.     

Self‐Assembling Supramolecular Hybrid Hydrogel Beads

With the goal of imposing shape and structure on supramolecular gels, we combine a low‐molecular‐weight gelator (LMWG) with the polymer gelator (PG) calcium alginate in a hybrid hydrogel. By imposing thermal and temporal control of the orthogonal gelation methods, the system either forms an extended interpenetrating network or core–shell‐structured gel beads—a rare example of a supramolecular gel formulated inside discrete gel spheres. The self‐assembled LMWG retains its unique properties within the beads, such as remediating Pd^II and reducing it in situ to yield catalytically active Pd⁰ nanoparticles. A single PdNP‐loaded gel bead can catalyse the Suzuki–Miyaura reaction, constituting a simple and easy‐to‐use reaction‐dosing form. These uniquely shaped and structured LMWG‐filled gel beads are a versatile platform technology with great potential in a range of applications.     

Modular Columnar Supramolecular Polymers as Scaffolds for Biomedical Applications

Self‐assembly of discotic molecules into supramolecular polymers offers a flexible approach for the generation of multicomponent one‐dimensional columnar architectures with tuneable biomedical properties. Decoration with ligands induces specific binding of the self‐assembled scaffold to biological targets. The modular design allows the easy co‐assembly of different discotics for the generation of probes for targeted imaging and cellular targeting with adjustable ligand density and composition.     

Concurring Chalcogen- and Halogen-Bonding Interactions in Supramolecular Polymers for Crystal Engineering Applications

The engineering of crystalline molecular solids through the simultaneous combination of distinctive non-covalent interactions is an important field of research, as it could allow chemist to prepare materials depicting multi-responsive properties. It is in this context that, pushed by a will to expand the chemical space of chalcogen-bonding interactions, a concept is put forward for which chalcogen- and halogen-bonding interactions can be used simultaneously to engineer multicomponent co-crystals. Through the rational design of crystallizable molecules, chalcogenazolo pyridine scaffold (CGP) modules were prepared that, bearing either a halogen-bond acceptor or donor at the 2-position, can interact with suitable complementary molecular modules undergoing formation of supramolecular polymers at the solid state. The recognition reliability of the CGP moiety to form chalcogen-bonded dimers allows the formation of heteromolecular supramolecular polymers through halogen-bonding interactions, as confirmed by single-crystal X-ray diffraction analysis.     

Impact of NDI-Core Substitution on the pH-Responsive Nature of Peptide-Tethered Luminescent Supramolecular Polymers

The pH-responsive nature of two self-assembled NDI-peptide amphiphile conjugates is reported. The diethoxy substituted NDI showed a pH-dependent assembly behaviour, as expected. In contrast, the isopropylamino- and ethoxy-substituted NDI based supramolecular polymer was stable at acidic and basic aqueous conditions. This finding highlights how subtle changes in the molecular design of π-stacked chromophore-peptide conjugates have a drastic impact on their equilibrium structure and ultimately functional properties.     

Supramolecular Architecture from the Self-assembly of One-dimensionalCoordination Polymers and Hydrogen Bonds

The synthesis and characterization of coordination polymers have been a rapid growth area in recent years. The coordination polymers consist of 1D chains, 2D sheets or 3D networks in which metal-organic building blocks connected via coordinate and hydrogen bonds. They received considerable attention because of their versatile intriguing architectures, topologies and potential applications in materials1,2 . As rigid rod-like spacers, 4,4'-bipyridine and its analogues have been used to give r…     

Self-Assembled Supramolecular Hybrid Hydrogel Beads Loaded with Silver Nanoparticles for Antimicrobial Applications

This Full Paper reports the formation of silver (Ag) NPs within spatially resolved two-component hydrogel beads, which combine a low-molecular-weight gelator (LMWG) DBS-CONHNH₂ and a polymer gelator (PG) calcium alginate. The AgNPs are formed through in situ reduction of Ag^I, with the resulting nanoparticle-loaded gels being characterised in detail. The antibacterial activity of the nanocomposite gel beads was tested against two drug-resistant bacterial strains, often associated with hospital-acquired infections: vancomycin-resistant Enterococcus faecium (VRE) and Pseudomonas aeruginosa (PA14), and the AgNP-loaded gels showed good antimicrobial properties against both types of bacteria. It is suggested that the gel bead format of these AgNP-loaded hybrid hydrogels makes them promising versatile materials for potential applications in orthopaedics or wound healing.     

Energetics of Competing Chiral Supramolecular Polymers

Chirality can have unexpected consequences including on properties other than spectroscopic. We show herein that a racemic mixture of bis-urea stereoisomers forms thermodynamically stable supramolecular polymers that result in a more viscous solution than for the pure stereoisomer. The origin of this macroscopic property was probed by characterizing the structure and stability of the assemblies. Both racemic and non-racemic bis-urea stereoisomers form two competing helical supramolecular polymers in solution: a double and a single helical structure at low and high temperature, respectively. The transition temperature between these assemblies, as probed by spectroscopic and calorimetric analyses, is strongly influenced by the composition (by up to 70 °C). A simple model that accounts for the thermodynamics of this system, indicates that the stereochemical defects (chiral mismatches and helix reversals) affect much more the stability of single helices. Therefore, the heterochiral double helical structure predominates over the single helical structure (whilst the opposite holds for the homochiral structures), which explains the aforementioned higher viscosity of the racemic bis-urea solution. This rationale constitutes a new basis to tune the macroscopic properties of the increasing number of supramolecular polymers reported to exhibit competing chiral nanostructures.     

Pyrazine Derivative as Supramolecular Host for Immobilization of Palladium Nanoparticles for Efficient Suzuki Coupling

Palladium nanoparticles (NPs) have been extensively explored as unique catalyst for carbon-carbon coupling reactions. Nonetheless, because of extreme tendency of nanoparticles to undergo agglomeration, the immobilization of these metal NPs on organic frameworks is an important area of research. The present investigation demonstrates the synthesis of pyrazine derivative PYZ - TA as a supramolecular host for holding co-released Pd NPs derived from the original catalyst (Pd(II)) under standard Suzuki coupling. Unprecedent, physical bars are not required to capture Pd NPs within the pores of supramolecular host. The as obtained catalyst PYZ - TA@Pd exhibits high potential to undergo self-assembly in solid as well as in liquid state. The PYZ - TA@Pd ensemble shows high catalytic activity and recyclability (up to seven cycles) in Suzuki-Miyaura coupling reactions using low palladium loading and provides the corresponding products in excellent yields (up to 98 %). Therefore, this study provides an efficient strategy to develop an easy to synthesize palladium centered solid catalyst through coordination between organic host and Pd NPs.     

Supramolecular Nanocycles Comprising β‐Cyclodextrin‐click‐Ferrocene Units: Rings of Rings of Rings

We applied 1,3‐dipolar cycloaddition to bind ethynylferrocene onto 6I‐azido‐6I‐deoxycyclomaltoheptaose under microwave assisted conditions. The process was investigated by ¹H NMR, FT‐IR spectroscopy, and MALDI‐TOF mass spectrometry. The ability of the synthesized compound to self‐organize to cyclic supramolecular structures was investigated by dynamic light scattering measurements and cryo‐transmission electron microscopy.

     

基于金属配位和主客体相互作用分级自组装构筑超分子凝胶

将金属配位和主客体相互作用引入到同1个超分子体系中,设计合成了2个超分子单体1和2.通过这2个超分子单体分级自组装形成的交联网状超分子聚合物构建了一种多重刺激响应性和良好自修复性能的超分子凝胶.同时,进一步将具有聚集诱导发光性能的四苯乙烯引入到这种超分子体系中,以赋予超分子体系新颖的发光性能.单体分子1是由中间为双苯并24-冠-8的冠醚连接2个四苯基乙烯荧光生色团,两端为2个三联吡啶分子构成的1个主体分子.单体分子1两端的三联吡啶基团可以与过渡金属Zn(OTf)2进行金属配位形成线型超分子聚合物3;而中间的冠醚基团与双二级铵盐客体分子2通过主客体相互作用进一步形成交联超分子聚合物4.当该交联超分子聚合物的浓度达到30 mmol/L时,可形成荧光超分子聚合物凝胶.通过核磁共振(1H-NMR和DOSY)与黏度等测试方法,证明了线形和交联超分子聚合物的形成,并进一步通过流变的测试证明了超分子聚合物凝胶的形成及其良好的自修复性能.除此之外,由于引入的主客体相互作用以及金属配位固有的刺激响应性,该荧光超分子聚合物凝胶表现出对温度、p H值、K+离子和竞争配体的刺激响应性能.