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1.
The self-assembly of discrete molecular entities into functional nanomaterials has become a major research area in the past decades. The library of investigated compounds has diversified significantly, while the field as a whole has matured. The incorporation of metal ions in the molecular design of the (supra-)molecular building blocks greatly expands the potential applications, while also offering a promising approach to control molecular recognition and attractive and/or repulsive intermolecular binding events. Hence, supramolecular polymerization of metal-containing monomers has emerged as a major research focus in the field. In this perspective article, we highlight recent significant advances in supramolecular polymerization of metal-containing monomers and discuss their implications for future research. Additionally, we also outline some major challenges that metallosupramolecular chemists (will) have to face to produce metallosupramolecular polymers (MSPs) with advanced applications and functionalities.

In this perspective article, we highlight recent significant advances in the self-assembly of metal-containing monomers and discuss their implications for future research.  相似文献   

2.
Predicting and designing systems with dynamic self-assembly properties in a spatiotemporal fashion is an important research area across disciplines ranging from understanding the fundamental non-equilibrium features of life to the fabrication of next-generation materials with life-like properties. Herein, we demonstrate a spatiotemporal dynamics pattern in the self-assembly behavior of a surfactant from an unorganized assembly, induced by adenosine triphosphate (ATP) and enzymes responsible for the degradation or conversion of ATP. We report the different behavior of two enzymes, alkaline phosphatase (ALP) and hexokinase (HK), towards adenosine triphosphate (ATP)-driven surfactant assembly, which also results in contrasting spatiotemporal dynamic assembly behavior. Here, ALP acts antagonistically, resulting in transient self-assemblies, whereas HK shows agonistic action with the ability to sustain the assemblies. This dynamic assembly behavior was then used to program the time-dependent emergence of a self-assembled structure in a two-dimensional space by maintaining concentration gradients of the enzymes and surfactant at different locations, demonstrating a new route for obtaining ‘spatial’ organizational adaptability in a self-organized system of interacting components for the incorporation of programmed functionality.

We have shown ATP-driven spatiotemporally distinct self-organization pattern of a surfactant in a two-dimensional space using enzymes, demonstrating a new route for obtaining ‘spatial’ organizational adaptability among interacting components.  相似文献   

3.
The bottom-up approach of supramolecular polymerization is an effective synthetic method for functional organic nanostructures. However, the uncontrolled growth and polydisperse structural outcome often lead to low functional efficiency. Thus, precise control over the structural characteristics of supramolecular polymers is the current scientific hurdle. Research so far has tended to focus on systems with inherent kinetic control by the presence of metastable state monomers either through conformational molecular design or by exploring pathway complexity. The need of the hour is to create generic strategies for dormant states of monomers that can be extended to different molecules and various structural organizations and dimensions. Here we venture to demonstrate chemical reaction-driven cooperative supramolecular polymerization as an alternative strategy for the controlled synthesis of organic two-dimensional nanostructures. In our approach, the dynamic imine bond is exploited to convert a non-assembling dormant monomer to an activated amphiphilic structure in a kinetically controlled manner. The chemical reaction governed retarded nucleation–elongation growth provides control over dispersity and size.

We report the kinetically controlled supramolecular polymerization of organic two-dimensional charge-transfer nanostructures via a chemical reaction (imine)-driven approach.  相似文献   

4.
Molecular recognition-driven self-assembly employing single-stranded DNA (ssDNA) as a template is a promising approach to access complex architectures from simple building blocks. Oligonucleotide-based nanotechnology and soft-materials benefit from the high information storage density, self-correction, and memory function of DNA. Here we control these beneficial properties with light in a photoresponsive biohybrid hydrogel, adding an extra level of function to the system. An ssDNA template was combined with a complementary photo-responsive unit to reversibly switch between various functional states of the supramolecular assembly using a combination of light and heat. We studied the structural response of the hydrogel at both the microscopic and macroscopic scale using a combination of UV-vis absorption and CD spectroscopy, as well as fluorescence, transmission electron, and atomic force microscopy. The hydrogels grown from these supramolecular self-assembly systems show remarkable shape-memory properties and imprinting shape-behavior while the macroscopic shape of the materials obtained can be further manipulated by irradiation.

Molecular recognition-driven self-assembly employing single-stranded DNA (ssDNA) as a template is a promising approach to access complex architectures from simple building blocks.  相似文献   

5.
Supramolecular copolymerizations offer attractive options to introduce structural and functional diversity in supramolecular polymer materials. Yet, general principles and structure–property relationships for rational comonomer design remain lacking. Here, we report on the supramolecular (co)aggregation of a phenylpyridine and bipyridine derivative of a recently reported biphenyl tetracarboxamide-based monomer. We show that both arylpyridines are poor monomers for supramolecular homopolymerizations. However, the two arylpyridines efficiently influence supramolecular polymers of a biphenyl-based polymer. The phenylpyridine derivatives primarily sequestrate biphenyl monomers, while the bipyridine intercalates into the polymers at high temperatures. Thereby, these two poorly homopolymerizing monomers allow for a fine control over the length of the biphenyl-based supramolecular polymers. As such, our results highlight the potential to control the structure and morphology of supramolecular polymers by tailoring the electronic properties of additives.

Supramolecular copolymerizations offer attractive options to introduce structural and functional diversity in supramolecular polymer materials.  相似文献   

6.
Controlling the reciprocity between chemical reactivity and supramolecular structure is a topic of great interest in the emergence of molecular complexity. In this work, we investigate the effect of a covalent reaction as a trigger to depolymerize a supramolecular assembly. We focus on the impact of an in situ thiol–ene reaction on the (co)polymerization of three derivatives of benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with cysteine, hexylcysteine, and alkyl side chains: Cys-BTA, HexCys-BTA, and a-BTA. Long supramolecular polymers of Cys-BTA can be depolymerized into short dimeric aggregates of HexCys-BTAvia the in situ thiol–ene reaction. Analysis of the system by time-resolved spectroscopy and light scattering unravels the fast dynamicity of the structures and the mechanism of depolymerization. Moreover, by intercalating the reactive Cys-BTA monomer into an unreactive inert polymer, the in situ thiol–ene reaction transforms the intercalator into a sequestrator and induces the depolymerization of the unreactive polymer. This work shows that the implementation of reactivity into supramolecular assemblies enables temporal control of depolymerization processes, which can bring us one step closer to understanding the interplay between non-covalent and covalent chemistry.

We report on the controlled depolymerization of supramolecular 1D polymers into well-defined dimers triggered by a covalent reaction on the side chains of the monomer.  相似文献   

7.
Recent advances in the research field of supramolecularly engineered dye aggregates have enabled the design of simple one-dimensional stacks such as fibers and of closed structures such as nanotoroids (nanorings). More complex and advanced supramolecular systems could potentially be designed using a molecule that is able to provide either of these distinct nanostructures under different conditions. In this study, we introduced bulky but strongly aggregating cholesterol units to a scissor-shaped azobenzene dyad framework, which affords either nanotoroids, nanotubes, or 1D fibers, depending on the substituents. This new dyad with two trans-azobenzene arms shows supramolecular polymorphism in its temperature-controlled self-assembly, leading to not only oligomeric nanotoroids as kinetic products, but also to one-dimensional fibers as thermodynamic products. This supramolecular polymorphism can also be achieved via photo-triggered self-assembly, i.e., irradiation of a monomeric solution of the dyad with two cis-azobenzene arms using strong visible light leads to the preferential formation of nanotoroids, whereas irradiation with weak visible light leads to the predominant formation of 1D fibers. This is the first example of a successful light-induced modulation of supramolecular polymorphism to produce distinctly nanostructured aggregates under isothermal conditions.

Introduction of the bulky yet strongly aggregating cholesterol units to an azobenzene dyad lead to a supramolecular polymorphism not only in its temperature-controlled but also in photo-triggered self-assembly, leading to toroids and helical fibers.  相似文献   

8.
Implementing chemical reactivity into synthetic supramolecular polymers based on π-conjugated molecules has been of great interest to create functional materials with spatiotemporal dynamic properties. However, the development of an in situ chemical reaction within supramolecular polymers is still in its infancy, because one needs to design optimal π-conjugated monomers having excellent reactivity under mild conditions possibly without byproducts or a catalyst. Herein we report the synthesis of a supramolecular polymer based on ethynyl core-substituted naphthalenediimide (S-NDI2) molecules that react with various amines quantitatively in a nonpolar solvent, without a catalyst, at 298 K. Most interestingly, the in situ reaction of the S-NDI2 supramolecular polymer with a linear aliphatic diamine proceeded much faster than the homogeneous reaction of a monomeric naphthalenediimide with the same diamine, affording diamine-linked S-NDI2 oligomers and polymers. The acceleration of in situ hydroamination was presumably due to rapid intra-supramolecular cross-linking between ethynyl and amino groups fixed in close proximity within the supramolecular polymer. Such intra-supramolecular cross-linking did not occur efficiently with an incompatible diamine. The systematic kinetic studies of in situ catalyst-free hydroamination within supramolecular polymers provide us with a useful, facile and versatile tool kit for designing dynamic supramolecular polymeric materials based on electron-deficient π-conjugated monomers.

A supramolecular polymer based on ethynyl core-substituted naphthalenediimides reacted with various amines quantitatively without a catalyst, exhibiting unconventional reaction kinetics and products.  相似文献   

9.
Chiral recognition and discrimination is not only of significance in biological processes but also a powerful method to fabricate functional supramolecular materials. Herein, a pair of heterochiral porous organic cages (HPOC-1), out of four possible enantiomeric products, with mirror stereoisomeric crystal structures were cleanly prepared by condensation occurring in the exclusive combination of cyclohexanediamine and binaphthol-based tetraaldehyde enantiomers. Nuclear magnetic resonance and luminescence spectroscopy have been employed to monitor the assembly process of HPOC-1, revealing the clean formation of heterochiral organic cages due to the enantioselective recognition of (S,S)-binaphthol towards (R,R)-cyclohexanediamine derivatives and vice versa. Interestingly, HPOC-1 exhibits circularly polarized luminescence and enantioselective recognition of chiral substrates according to the circular dichroism spectral change. Theoretical simulations have been carried out, rationalizing both the enantioselective assembly and recognition of HPOC-1.

Heterochiral organic cages based on enantioselective self-assembly of binary chiral components have been prepared, exhibiting circularly polarized luminescence property and enantioselective recognition ability towards chiral substrates according to the circular dichroism spectral change.  相似文献   

10.
Charge transfer (CT) interaction induced formation of a hierarchical supramolecular assembly has attracted attention due to its wide diversity of structural and functional characteristics. In the present work, we report the generation of green luminescent microspheres from the charge transfer interaction induced co-assembly of a bis-naphthyl dipicolinic amide (DPA) derivative with tetracyanobenzene (TCNB) for the first time. The properties of these self-assemblies were studied both in solution and the solid-state using spectroscopic and a variety of microscopy techniques. The X-ray crystal structure analysis showed a mixed stack arrangement of DPA and TCNB. The molecular orbital and energy level calculations confirm the charge transfer complex formation between DPA and TCNB. Furthermore, energy transfer was observed from the green luminescent CT complex to a red-emitting dye, pyronin Y, in the microsphere matrix, leading to the formation of a light-harvesting tri-component self-assembly.

Green luminescent microspheres, generated via charge-transfer interaction-induced hierarchical co-assembly of a bis-naphthyl dipicolinic amide derivative and tetracyanobenzene, transfer energy to long-wave emitting dye.  相似文献   

11.
Beyond the AIE (aggregation-induced emission) phenomenon in small molecules, supramolecules with AIE properties have evolved in the AIE family and accelerated the growth of supramolecular application diversity. Inspired by its mechanism, particularly the RIV (restriction of intramolecular vibrations) process, a feasible strategy of constructing an AIE-supramolecular cage based on the oxidation of sulfur atoms and coordination of metals is presented. In contrast to previous strategies that used molecular stacking to limit molecular vibrations, we achieved the desired goal using the synergistic effects of coordination-driven self-assembly and oxidation. Upon assembling with zinc ions, S1 was endowed with a distinct AIE property compared with its ligand L1, while S2 exhibited a remarkable fluorescence enhancement compared to L2. Also, the single cage-sized nanowire structure of supramolecules was obtained via directional electrostatic interactions with multiple anions and rigid-shaped cationic cages. Moreover, the adducts of zinc porphyrin and supramolecules were investigated and characterized by 2D DOSY, ESI-MS, TWIM-MS, UV-vis, and fluorescence spectroscopy. The protocol described here enriches the ongoing research on tunable fluorescence materials and paves the way towards constructing stimuli-responsive luminescent supramolecular cages.

Beyond the AIE (aggregation-induced emission) phenomenon in small molecules, supramolecules with AIE properties have evolved in the AIE family and accelerated the growth of supramolecular application diversity.  相似文献   

12.
Controlling supramolecular self-assembly across multiple length scales to prepare gels with localised properties is challenging. Most strategies concentrate on fabricating gels with heterogeneous components, where localised properties are generated by the stimuli-responsive component. Here, as an alternative approach, we use a spiropyran-modified surface that can be patterned with light. We show that light-induced differences in surface chemistry can direct the bulk assembly of a low molecular weight gelator, 2-NapAV, meaning that mechanical gel properties can be controlled by the surface on which the gel is grown. Using grazing incidence X-ray diffraction and grazing incidence small angle X-ray scattering, we demonstrate that the origin of the different gel properties relates to differences in the architectures of the gels. This provides a new method to prepare a single domain (i.e., chemically homogeneous) hydrogel with locally controlled (i.e., mechanically heterogeneous) properties.

A mechanical pattern is created in a hydrogel film by pre-patterning the underlying surface chemistry. This allows spatial variation of the viscous component of the gel, controlling dissipative forces in the gel film without altering gel chemistry.  相似文献   

13.
Photoisomeric supramolecular assemblies have drawn enormous attention in recent years. Although it is a general rule that photoisomerization from a less to a more distorted isomer causes the destruction of assemblies, this photoisomerization process inducing a converse transition from irregular aggregates to regular assemblies is still a great challenge. Here, we report a converse sol-to-gel transition derived from the planar to nonplanar photoisomer conversion, which is in sharp contrast to the conventional light-induced gel collapse. A well-designed acylhydrazone-linked monomer is exploited as a photoisomer to realize the above-mentioned phase transition. In the monomer, imine is responsible for transcis interconversion and amide generates intermolecular hydrogen bonds enabling the photoisomerization-driven self-assembly. The counterintuitive feature of the sol-to-gel transition is ascribed to the partial transcis photoisomerization of acylhydrazone causing changes in stacking mode of monomers. Furthermore, the reversible phase transition is applied in the valves formed in situ in microfluidic devices, providing fascinating potential for miniature materials.

A converse sol-to-gel transition system based on transcis photoisomerization of acylhydrazone-based supramolecular assemblies has been sucessfully established, which was applied in the gel-based microvalves that can in situ control flow by light.  相似文献   

14.
Kinetic control over structures and functions of complex assembly systems has aroused widespread interest. Understanding the complex pathway and transient intermediates is helpful to decipher how multiple components evolve into complex assemblies. However, for supramolecular polymerizations, thorough and quantitative kinetic analysis is often overlooked. Challenges remain in collecting the information of structure and content of transient intermediates in situ with high temporal and spatial resolution. Here, the unsolved evolution mechanism of a classical self-sorting supramolecular copolymerization system was addressed by employing multidimensional NMR techniques coupled with a microfluidic technique. Unexpected complex pathways were revealed and quantitatively analyzed. A counterintuitive pathway involving polymerization through the ‘error-correction’ of non-polymerizable transient intermediates was identified. Moreover, a ‘non-classical’ step-growth polymerization process controlled by the self-sorting mechanism was unraveled based on the kinetic study. Realizing the existence of transient intermediates during self-sorting can encourage the exploitation of this strategy to construct kinetic steady state assembly systems. Moreover, the strategy of coupling a microfluidic technique with various characterization techniques can provide a kinetic analysis toolkit for versatile assembly systems. The combined approach of coupling thermodynamic and kinetic analyses is indispensable for understanding the assembly mechanisms, the rules of emergence, and the engineering of complex assembly systems.

Polymerization through the ‘error-correction’ of non-polymerizable transient intermediates was identified in a classical self-sorting supramolecular copolymerization system by employing NMR coupled with a microfluidic technique.  相似文献   

15.
Multivalent supramolecular assemblies have recently attracted extensive attention in the applications of soft materials and cell imaging. Here, we report a novel multivalent supramolecular assembly constructed from 4-(4-bromophenyl)pyridine-1-ium bromide modified hyaluronic acid (HABr), cucurbit[8]uril (CB[8]) and laponite® clay (LP), which could emit purely organic room-temperature phosphorescence (RTP) with a phosphorescence lifetime of up to 4.79 ms in aqueous solution via multivalent supramolecular interactions. By doping the organic dyes rhodamine B (RhB) or sulfonated rhodamine 101 (SR101) into the HABr/CB[8]/LP assembly, phosphorescence energy transfer was realized with high transfer efficiency (energy transfer efficiency = 73–80%) and ultrahigh antenna effect (antenna effect value = 308–362) within the phosphorescent light harvesting system. Moreover, owing to the dynamic nature of the noncovalent interactions, a wide-range spectrum of phosphorescence energy transfer outputs could be obtained not only in water but also on filter paper and a glass plate by adjusting the donor–acceptor ratio and, importantly, white-light emission was obtained, which could be used in the application of information encryption.

An ultralong lifetime supramolecular assembly was constructed via multivalent supramolecular interactions and achieved phosphorescence light harvesting. Multicolor (including white) broad-spectrum outputs could be achieved in water and also on filter paper and a glass plate.  相似文献   

16.
This study uses X-ray crystallography, theory and Langmuir isotherm analysis to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes. Favoured conformations retain the more polar triaxial C–F bond arrangement of the all-cis 2,3,4,5,6-pentafluorocyclohexyl ring systems with the alkyl substituent adopting an equatorial orientation, and accommodating strong supramolecular interactions between rings. Langmuir isotherm analysis on a water subphase of a long chain fatty acid and alcohol carrying terminal all-cis 2,3,4,5,6-pentafluorocyclohexyl rings do not show any indication of monolayer assembly relative to their cyclohexane analogues, instead the molecules appear to aggregate and form higher molecular assemblies prior to compression. The study indicates the power and potential of this ring system as a motif for ordering supramolecular assembly.

Theory and Langmuir isotherm analysis was used to explore the conformations and molecular packing of alkyl all-cis 2,3,4,5,6-pentafluorocyclohexyl motifs, which are prepared by direct aryl hydrogenations from alkyl- or vinyl-pentafluoroaryl benzenes.  相似文献   

17.
The efficient preparation of chiral porous organic cages (POCs) with specific functions is challenging, and their application in asymmetric catalysis has not previously been explored. In this work, we have achieved the construction of chiral POCs based on a supramolecular tetraformyl-resorcin[4]arene scaffold with different chiral proline-modified diamine ligands and utilizing dynamic imine chemistry. The incorporation of V-shaped or linear chiral diamines affords the [4 + 8] square prism and [6 + 12] octahedral POCs respectively. The appended chiral proline moieties in such POCs make them highly active supramolecular nanoreactors for asymmetric aldol reactions, delivering up to 92% ee. The spatial distribution of chiral catalytic sites in these two types of POCs greatly affects their catalytic activities and enantioselectivities. This work not only lays a foundation for the asymmetric catalytic application of chiral POCs, but also contributes to our understanding of the catalytic function of biomimetic supramolecular systems.

Two calix[4]resorcinarene-based chiral POCs with different self-assembly forms were constructed. The difference in the spatial distribution of chiral organocatalytic sites leads to the two chiral POCs exhibiting distinct stereoselectivities.  相似文献   

18.
Well-studied cycloparaphenylenes (CPPs) correspond to the simplest segments of armchair CNTs, whereas the corresponding macrocyclic oligophenylene strip of zigzag CNTs is still missing. Herein, we present two series of conjugated macrocycles (CM2PP and CN2PP) containing two meta-phenylene or 2,7-naphthylene units facing each other in the strip. CM2PP and CN2PP can be regarded as the shortest cyclic primitive segments of zigzag CNTs. They were synthesized by gold-mediated dimerization and unambiguously characterized. They adopted the tubular structures and can further pack into one-dimensional supramolecular nanotubes. In particular, the supramolecular nanotube of CM2P4P mimics the CNT(9, 0) structure. Structural analysis and theoretical calculation accounted for the reduced ring strain in CM2PPs and CN2PPs. CM2PPs and CN2PPs exhibited a large optical extinction coefficient and high photoluminescence quantum yield. CN2P8P can accommodate fullerene C60, forming a Saturn-like C60@CN2P8P complex, a mimic structure of zigzag CNT peapods.

Two types of macrocycles were synthesized by gold-mediated dimerization, representing the phenylene cutouts of zigzag carbon nanotubes. These macrocycles showed intriguing optical and supramolecular assembly properties.  相似文献   

19.
Progressive solute-rich polymer phase transitions provide pathways for achieving ordered supramolecular assemblies. Intrinsically disordered protein domains specifically regulate information in biological networks via conformational ordering. Here we consider a molecular tagging strategy to control ordering transitions in polymeric materials and provide a proof-of-principle minimal peptide phase network captured with a dynamic chemical network.

Substrate initiated assembly of a dynamic chemical network.  相似文献   

20.
The transformation from disorder to order in self-assembly is an autonomous entropy-decreasing process. The spatial organization of nanoscale anisotropic building blocks involves the intrinsic heterogeneity in three dimensions and requires sufficiently precise control to coordinate intricate interactions. Only a few approaches have been shown to achieve the anisotropic extension from components to assemblies. Here, we demonstrate the ability to engineer three-dimensional low-entropy lattices at the nucleotide level from modular DNA origami frames. Through the programmable DNA bridging strategy, DNA domains of the same composition are periodically arranged in the crystal growth directions. We combine the site-specific positioning of guest nanoparticles to reflect the anisotropy control, which is validated by small-angle X-ray scattering and electron microscopy. We expect that our DNA origami-mediated crystallization method will facilitate both the exploration of refined self-assembly platforms and the creation of anisotropic metamaterials.

Through the bridging principle, DNA origami building blocks are integrated into ordered self-assembled structures. Periodically arranged DNA domains can locate the nanoparticles in a uniform site to achieve precise control of the contents.  相似文献   

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