Simultaneous Chiral Fixation and Chiral Regulation Endowed by Dynamic Covalent Bonds

The construction of chiral superstructures through the self-assembly of non-chiral polymers usually relies on the interplay of multiple non-covalent bonds, which is significantly limited by the memory ability of induced chirality. Although the introduction of covalent crosslinking can undoubtedly enhance the stability of chiral superstructures, the concurrent strong constraining effect hinders the application of chirality-smart materials. To address this issue, we have made a first attempt at the reversible fixation of supramolecular chirality by introducing dynamic covalent crosslinking into the chiral self-assembly of side-chain polymers. After chiral induction, the reversible [2+2] cycloaddition reaction of the cinnamate group in the polymer chains can be further controlled by light to manipulate inter-chain crosslinking and decrosslinking. Based on this photo-programmable and dynamic chiral fixation strategy, a novel pattern-embedded storage mechanism of chiral polymeric materials was established for the first time.     

Toward self-assembled surface-mounted prismatic altitudinal rotors. A test case: molecular rectangle

[structure: see text] A self-assembly path toward prismatic molecular rotors based on transversely reactive terminally metalated molecular rods and pyridine-terminated star connectors is outlined. The concept is tested on the assembly of the biphenyl rod [Ph(2)P(CH(2))(3)PPh(2)Pt(+)-C(6)H(4)-C(6)H(4)-Pt(+)[Ph(2)P(CH(2))(3)PPh(2)] and 4,4'-bipyridyl into a molecular rectangle, fully characterized by NMR and MS, including diffusion-ordered NMR and collision-induced dissociation MS.     

Template-directed synthesis employing reversible imine bond formation

The imine bond--formed by the reversible condensation of an amine and an aldehyde--and its applications as a dynamic covalent bond in the template-directed synthesis of molecular compounds, will be the focus of this tutorial review. Template-directed synthesis--or expressed another way, supramolecular assistance to covalent synthesis--relies on the use of reversible noncovalent bonding interactions between molecular building blocks in order to preorganise them into a certain relative geometry as a prelude to covalent bond formation to afford the thermodynamically preferred product. The use of this so-called dynamic covalent chemistry (DCC) in templated reactions allows for an additional amount of reversibility, further eliminating potential kinetic products by allowing the covalent bonds that are formed during the template-directed reaction to be 'proofread for errors', thus making it possible for the reaction to search out its thermodynamic minimum. The marriage of template-directed synthesis with DCC has allowed chemists to construct an increasingly complex collection of compounds from relatively simple precursors. This new paradigm in organic synthesis requires that each individual piece in the molecular self-assembly process is preprogrammed so that the multiple recognition events expressed between the pieces are optimised in a highly cooperative manner in the desired product. It offers an extremely simple way of making complex mechanically interlocked compounds--e.g., catenanes, rotaxanes, suitanes, Borromean rings and Solomon knots--from relatively simple precursors.     

Covalently attached sandwich structure from colloidal particles and diazoresin

A covalently attached sandwich structure between layers and particles has been fabricated from z.sbnd;COOH-containing copolymer latex particles and z.sbnd;N(2)(+)-containing polymers by self-assembly combined with a UV irradiation technique. The ionic bonds involving the layers and particles change to covalent bonds under UV irradiation and the sandwich structure become very stable toward polar organic solvents and electrolyte aqueous solutions.     

Toward self-assembled surface-mounted prismatic altitudinal rotors. A test case: trigonal and tetragonal prisms

[structure: see text] A self-assembly path toward prismatic molecular rotors based on transversely reactive terminally metalated molecular rods and pyridine-terminated star connectors has been extended. The concept has been tested on the assembly of trigonal and tetragonal prisms from the biphenyl rod, [Ph2P(CH2)3PPh2]Pt+ -C6H4-C6H4-Pt+ [Ph2P(CH2)3PPh2], and the star-shaped connectors, 1,3,5-tris(4-ethynylpyridyl)benzene and [tetrakis(4-pyridyl)cyclobutadiene]cyclopentadienylcobalt, respectively. The prisms have been fully characterized by NMR and MS, including diffusion-ordered NMR and collision-induced dissociation, and their chiral structures optimized by molecular mechanics are discussed.     

Formation of a Macrocycles‐in‐a‐Macrocycle Superstructure with All‐gauche Conformation by Reversible Radical Association

The formation of an unprecedented macrocycles‐in‐a‐macrocycle (MIM) superstructure by reversible radical–radical association of a triphenylamine based monomer terminated with three dicyanomethyl radicals is presented. The reaction yield is nearly quantitative and the obtained macrocycle contains three small dimeric macrocycles according to X‐ray crystallographic analysis. The six monomer molecules are linked by nine long dynamic covalent C(sp³)?C(sp³) bonds that all adopt a gauche conformation. Such a conformation favors the formation of a MIM structure rather than a 2D network with an all‐anti conformation. Two enantiomers with left‐/ right‐handed chirality exist in the single crystals of the superstructure.     

On the contribution of covalent and ionic species to the chain growth. Monte Carlo simulations and theoretical considerations

Contributions of the covalent and ionic species to the chain building in cationic reversible polymerizations are analyzed by means of Monte Carlo simulations and by solving the formulated set of equations. The validity of the equation for the contribution of covalent propagation, derived for reversible polymerization with simplifying assumptions, is discussed. It is shown that repeating units incorporated into the chain by covalent propagations are distributed uniformly only when direct monomer insertion into covalent bonds is not possible, or when intramolecular interconversion of covalent and ionic species is very fast in comparison with propagation.     

Demonstration of α-helical structure of peptides tethered to gold surfaces using surface infrared and circular dichroic spectroscopies

Gold and quartz surfaces terminated in an alkane thiol self-assembled monolayer (SAM) that were partially terminated with azide were reacted with a helical peptide containing two alkyne groups in a Cu(I)-catalyzed Huisgen cycloaddition. Surface grazing incidence angle reflection-absorption infrared spectroscopy (GRAS-IR) was used to determine that when the Au surface was terminated with 25% of the monolayer containing azide groups, 92% of available azide groups reacted with the peptide. The majority of peptides reacted with both alkynes, resulting in peptides tethered to the surface through two covalent bonds. This was confirmed by comparison to a control peptide containing only one reactive alkyne group. Surface circular dichroic (CD) spectroscopy showed that while the helical structure of the peptide was distorted in the reaction solution, α-helical structure was induced when tethered on the SAM functionalized Au surface. Demonstration of the preservation of desired secondary structure of helical elements at a chemically functionalized surface is an important advance in preparing robust biologically mimetic surfaces to integrate functioning proteins into inorganic materials.     

Supramolecular concepts and new techniques in mechanochemistry: cocrystals, cages, rotaxanes, open metal-organic frameworks

Mechanochemical reactions effected by milling or grinding are an attractive means to conduct chemical reactions dependent on molecular recognition and to systematically explore different modes of molecular self-assembly. The natural relationship between milling mechanochemistry and supramolecular chemistry arises primarily from the ability to avoid bulk solvent, which simultaneously avoids limitations of solution-based chemistry, such as solubility, solvent complexation, or solvolysis, and makes the resulting process highly environmentally friendly. This tutorial review highlights the use of mechanochemistry for the synthesis of supramolecular targets in the solid state, such as molecular hydrogen- or halogen-bonded complexes, molecular and supramolecular cages, open frameworks and interlocked architectures. It is also demonstrated that the molecular self-assembly phenomena that are well-established in solution chemistry, such as reversible binding through covalent or non-covalent bonds, thermodynamic equilibration and structure templating, are also accessible in milling mechanochemistry through recently developed highly efficient methodologies such as liquid-assisted grinding (LAG) or ion- and liquid-assisted grinding (ILAG). Also highlighted are the new opportunities arising from the marriage of concepts of supramolecular and mechanochemical synthesis, including organocatalysis, deracemisation and discovery of new molecular recognition motifs.     

Self-Assembly of Hexagonal Rod Arrays Based on Capillary Forces

A series of well-ordered, extended mesostructures has been generated from hexagonal polyurethane rods (15x3.2 mm) by self-assembly using capillary forces. The surface of one or more sides of the rods was rendered hydrophilic by exposure to an oxygen plasma. This modification determined the pattern of hydrophobic and hydrophilic faces; the hydrophobic sides were coated with a thin film of a hydrophobic lubricant. Agitation of the rods in an approximately isodense aqueous environment resulted in their self-assembly, in a process reflecting the action of capillary forces, into an array whose structure depends on the pattern of hydrophobic sides; capillarity also aligned the ends of the rods. We also carried out experiments in reaction chambers that restricted the motion of the rods; this restriction served to increase the size and regularity of the assemblies. Copyright 2000 Academic Press.     

Reversible Supracolloidal Self-Assembly of Cobalt Nanoparticles to Hollow Capsids and Their Superstructures

The synthesis and spontaneous, reversible supracolloidal hydrogen bond-driven self-assembly of cobalt nanoparticles (CoNPs) into hollow shell-like capsids and their directed assembly to higher order superstructures is presented. CoNPs and capsids form in one step upon mixing dicobalt octacarbonyl (Co₂CO₈) and p-aminobenzoic acid (pABA) in 1,2-dichlorobenzene using heating-up synthesis without additional catalysts or stabilizers. This leads to pABA capped CoNPs (core ca. 5 nm) with a narrow size distribution. They spontaneously assemble into tunable spherical capsids (d≈50–200 nm) with a few-layered shells, as driven by inter-nanoparticle hydrogen bonds thus warranting supracolloidal self-assembly. The capsids can be reversibly disassembled and reassembled by controlling the hydrogen bonds upon heating or solvent exchanges. The superparamagnetic nature of CoNPs allows magnetic-field-directed self-assembly of capsids to capsid chains due to an interplay of induced dipoles and inter-capsid hydrogen bonds. Finally, self-assembly on air–water interface furnishes lightweight colloidal framework films.     

乳胶颗粒与硝基重氮树脂的自组装

高分子通过静电、氢键、电荷转移等的自组装 ,尤其是静电自组装已有大量报道[1] .带重氮基(Ｎ+2 )高分子 (重氮树脂 ,ＤＲ)自组装的特点是形成组装膜的弱键 ,光照下能转变为共价键 ,不稳定的膜变成稳定的膜[2 ] .乳胶颗粒的组装 ,因胶体晶体、光子晶体的进展 ,越来越受关注[3 ] ,国内也有一些评述文章[4 ,5] .就胶体晶体而言 ,用它作模板 ,几乎能制备包括无机、有机、金属、陶瓷的各种多孔材料 .自然界的蛋白石 (Ｏｐａｌｓ)是ＳｉＯ2 颗粒有序沉积物中 ,渗入水溶性硅酸盐 ,再在其中固化形成的 .按照自然形成蛋白石的模式 ,从胶体晶体复制 ,…     

Controlling Covalent Connection and Disconnection with Light

The on‐going need for feature miniaturization and the growing complexity of structures for use in nanotechnology demand the precise and controlled formation of covalent bonds at the molecular level. Such control requires the use of external stimuli that offer outstanding spatial, temporal, as well as energetic resolution. Thus, photoaddressable switches are excellent candidates for creating a system that allows reversible photocontrol over covalent chemical connection and disconnection. Here we show that the formation of covalent bonds between two reagents and their scission in the resulting product can be controlled exclusively by illumination with differently colored light. A furyl‐substituted photoswitchable diarylethene was shown to undergo a reversible Diels–Alder reaction with maleimide to afford the corresponding Diels–Alder adduct. Our system is potentially applicable in any field already relying on the benefits of reversible Diels–Alder reactions.     

Towards mechanically-linked polymers

This short review describes the progress which is being made towards the self-assembly of mechanically-linked polymers. A new concept in polymer synthesis - self-assembly - is demonstrated to have the potential to create novel high molecular weight polymers which possess repeat units that do not just consist of a main chain backbone built up of entirely covalent bonds, but are constructed of mechanical linkages comprised of catenane and rotaxane motifs.     

Dynamic covalent chemistry

Dynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, however, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is noncovalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.     

Reversible Covalent End-Capping of Collagen Model Peptides

The combination of supramolecular aggregation of collagen model peptides with reversible covalent end-capping of the formed triple helix in a single experimental set-up yielded minicollagens, which were characterized by a single melting temperature. In spite of the numerous possible reaction intermediates, a specific synthetic collagen with a leading, middle and trailing strand is formed in a highly cooperative self-assembly process.     

Pathway-dependent self-assembly of perylene diimide/peptide conjugates in aqueous medium

Most molecular self-assembly strategies involve equilibrium systems, leading to a single thermodynamic product as a result of weak, reversible non-covalent interactions. Yet, strong non-covalent interactions may result in non-equilibrium self-assembly, in which structural diversity is achieved by forming several kinetic products based on a single covalent building block. We demonstrate that well-defined amphiphilic molecular systems based on perylene diimide/peptide conjugates exhibit kinetically controlled self-assembly in aqueous medium, enabling pathway-dependent assembly sequences, in which different organic nanostructures are evolved in a stepwise manner. The self-assembly process was characterized using UV/Vis circular dichroism (CD) spectroscopy, and cryogenic transmission electron microscopy (cryo-TEM). Our findings show that pathway-controlled self-assembly may significantly broaden the methodology of non-covalent synthesis.     

Three-dimensional self-assembly of metallic rods with submicron diameters using magnetic interactions

Metallic rods with submicron diameters that contain disklike ferromagnetic sections self-assemble into highly stable, hexagonally close-packed arrays of rods. The rods were fabricated by electrodeposition in porous alumina membranes and comprised alternating sections of gold and nickel. The thicknesses of the ferromagnetic nickel sections were approximately one-half the diameter of the rods (400 nm); this geometry orients the "easy" axis of magnetization perpendicular to the long axis of the rod. After magnetization of the rods with a rare-earth magnet, followed by sonication of the suspension, the rods spontaneously assembled into three-dimensional (3D) bundles that, on average, contained 15-30 rods. A macroscopic model of the rods suggests that the most stable orientation of the magnetic dipoles for rods in a defect-free, hexagonally close-packed arrangement is in concentric rings with the dipoles oriented head-to-tail. This configuration minimizes the energy of the bundle and does not generate a net dipole for the structure. This work provides a simple demonstration that magnetic interactions between ferromagnetic objects can direct and stabilize the formation of ordered, 3D structures by self-assembly.     

A Versatile Approach to Dynamic Amide Bond Formation with Imine Nucleophiles

Dynamic covalent chemistry has rapidly become an important approach to access supramolecular structures. While the products generated in these reactions are held together by covalent bonds, the reversible nature of the transformations can limit the utility of many these systems in creating robust materials. We describe herein a method to form stable and commonly employed amide bonds by exploiting the reversible coupling of imines and acyl chlorides. The reaction employs easily accessible reagents, is dynamic under ambient conditions, without catalysts, and can be trapped with simple hydrolysis. This offers an approach to create broad families of amide products under thermodynamic control, including the selective formation of amide macrocycles or polymers.