Supramolecular Crystal Engineering at the Solid–Liquid Interface from First Principles: Toward Unraveling the Thermodynamics of 2D Self‐Assembly

The formation of highly ordered 2D supramolecular architectures self‐assembled at the solid–solution interfaces is subject to complex interactions between the analytes, the solvent, and the substrate. These forces have to be mastered in order to regard self‐assembly as an effective bottom‐up approach for functional‐device engineering. At such interfaces, prediction of the thermodynamics governing the formation of spatially ordered 2D arrangements is far from being fully understood, even for the physisorption of a single molecular component on the basal plane of a flat surface. Two recent contributions on controlled polymorphism and nanopattern formation render it possible to gain semi‐quantitative insight into the thermodynamics of physisorption at interfaces, paving the way towards 2D supramolecular crystal engineering. Although in these two works different systems have been chosen to tackle such a complex task, authors showed that the chemical design of molecular building blocks is not the only requirement to fulfill when trying to preprogram self‐assembled patterns at the solid–liquid interface.     

Photoresponsive Cucurbit[8]uril‐Mediated Adhesion of Bacteria on Supported Lipid Bilayers

In this work, the development of a photoresponsive platform for the presentation of bioactive ligands to study receptor–ligand interactions has been described. For this purpose, supramolecular host–guest chemistry and supported lipid bilayers (SLBs) have been combined in a microfluidic device. Quartz crystal microbalance with dissipation monitoring (QCM‐D) studies on methyl viologen (MV)‐functionalized oligo ethylene glycol‐based self‐assembled monolayers, gel and liquid‐state SLBs have been compared for their nonfouling properties in the case of ConA and bacteria. In combination with bacterial adhesion test, negligible nonspecific bacterial adhesion is observed only in the case of methyl‐viologen‐modified liquid‐state SLBs. Therefore, liquid‐state SLBs have been identified as most suitable for studying specific cell interactions when MV is incorporated as a guest on the surface. The photoswitchable supramolecular ternary complex is formed by assembling cucurbit[8]uril (CB[8]) and an azobenzene–mannose conjugate (Azo–Man) onto MV‐functionalized liquid‐state SLBs and the assembly process has been characterized using QCM‐D and fluorescence techniques. Mannose has been found to enable binding of E. coli via cell‐surface receptors on the nonfouling supramolecular SLBs. Optical switching of the azobenzene moiety allows us to “erase” the bioactive surface after bacterial binding, providing the potential to develop reusable sensors. Localized photorelease of bacterial cells has also been shown indicating the possibility of optically guiding cellular growth, migration, and intercellular interactions.     

Atomically Precise Prediction of 2D Self‐Assembly of Weakly Bonded Nanostructures: STM Insight into Concentration‐Dependent Architectures

A joint experimental and computational study is reported on the concentration‐dependant self‐assembly of a flat C₃‐symmetric molecule on a graphite surface. As a model system a tripodal molecule, 1,3,5‐tris(pyridin‐3‐ylethynyl)benzene, has been chosen, which can adopt either C_3h or C_s symmetry when planar, as a result of pyridyl rotation along the alkynyl spacers. Density functional theory (DFT) simulations of 2D nanopatterns with different surface coverage reveal that the molecule can generate different types of self‐assembled motifs. The stability of fourteen 2D patterns and the influence of concentration are analyzed. It is found that ordered, densely packed monolayers and 2D porous networks are obtained at high and low concentrations, respectively. A concentration‐dependent scanning tunneling microscopy (STM) investigation of this molecular self‐assembly system at a solution/graphite interface reveals four supramolecular motifs, which are in perfect agreement with those predicted by simulations. Therefore, this DFT method represents a key step forward toward the atomically precise prediction of molecular self‐assembly on surfaces and at interfaces.     

Light‐Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid–Liquid Interface

The use of a bottom‐up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light‐responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans‐to‐cis photoisomerization of a photoswitchable metallopolymer that self‐assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans‐azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans‐based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive “smart” surfaces organized with an atomic precision.     

Superstructures of Self‐Organizing Thiophenes

The self‐assembling properties of π‐conjugated oligo‐, poly‐, and cyclothiophenes (see Figure) have been studied with different techniques. Scanning tunneling microscopy on perfectly ordered two‐dimensional monolayers at the solution–HOPG (highly oriented pyrolytic graphite) interface has successfully been applied. The submolecular resolution achieved in the STM images provides valuable lattice and molecular information. Supported by X‐ray structure analyses of the 3D bulk material and by theoretical calculations, molecular conformations, molecule–molecule, and molecule–substrate interactions of the oligo‐, poly‐, and cyclomers have been analyzed and discussed.     

Covalently Linked Perylene Diimide–Polydiacetylene Nanofibers Display Enhanced Stability and Photocurrent with Reversible FRET Phenomenon

Because of their unique structural and optical properties, 1D perylene diimide (PDI) derivatives have gained attention for use in optoelectronic devices. However, PDI‐containing self‐assembled supramolecular systems often are of limited use because they have supramolecular architectures that are held together by weak noncovalent π–π stacking, hydrogen bonding, and hydrophobic interactions. As a result, they are intrinsically unstable under solution‐processing conditions. To overcome this limitation, a polydiacetylene (PDA)‐based strategy is developed to construct a solvent‐resistant and stable PDI assembly. For this purpose, first the monomer PDI–BisDA is generated, in which two polymerizable diacetylene (DA) units are covalently linked to a PDI core. Importantly, 254 nm UV irradiation of self‐assembled PDI–BisDA nanofibers forms solvent‐resistant and stable PDI–PDA fibers. Owing to the presence of PDA, the generated polymer fibers display an increased photocurrent. In addition, the existence of PDA and PDI moieties in the fiber leads to the occurrence of switchable on–off fluorescence resonance energy transfer (FRET) between the PDI and reversibly thermochromic PDA chromophores.     

Charge‐Transfer Supra‐Amphiphiles Built by Water‐Soluble Tetrathiafulvalenes and Viologen‐Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions

In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge–transfer interaction and supra‐amphiphile self‐assembling in aqueous phase. The charge–transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger‐transfer absorption. ¹H NMR and electrospray ionizsation mass spectrometry (ESI‐MS) analyses also indicate supra‐amphiphiles are formed by the combination of TTFs and MVs head group through charge–transfer interaction and Coulombic force. X‐ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra‐amphiphile‐driven organic‐AuNPs assembly system. AuNPs could be assembled into 1D–3D structures by adding different amount of MVs.     

Supramolecular Polymers: Rigid Dimers Formed through Strong Interdigitated H‐Bonds Yield Compact 1D Supramolecular Helical Polymers (Small 3/2011)

Hierarchical self‐assembly of small abiotic molecular modules interacting through noncovalent forces is increasingly being used to generate functional structures and materials for electronic, catalytic, and biomedical applications. The greatest control over the geometry in H‐bond supramolecular architectures, especially in H‐bonded supramolecular polymers, can be achieved by using conformationally rigid molecular modules undergoing self‐assembly through strong H‐bonds. Their binding strength depends on the multiplicity of the H‐bonds, the nature of donor/acceptor pairs and their secondary attractive/repulsive interactions. Here a functionalized molecular module is described, which is capable of self‐associating through self‐complementary H‐bonding patterns comprising four strong and two medium‐strength H‐bonds to form dimers. The self‐association of these phenylpyrimidine‐based dimers through directional H‐bonding between two lateral pyridin‐2(1H)‐one units of neighboring molecules allows the formation of highly compact 1D supramolecular polymers by self‐assembly on graphite. A concentration‐dependent study by scanning tunneling microscopy at the solid–liquid interface, corroborated by dispersion‐corrected density functional studies, reveals the controlled generation of either linear supramolecular 2D arrays, or long helical supramolecular polymers with a high shape persistence.     

Microfluidics‐Assisted Assembly of Injectable Photonic Hydrogels toward Reflective Cooling

Development of fast curing and easy modeling of colloidal photonic crystals is highly desirable for various applications. Here, a novel type of injectable photonic hydrogel (IPH) is proposed to achieve self‐healable structural color by integrating microfluidics‐derived photonic supraballs with supramolecular hydrogels. The supramolecular hydrogel is engineered via incorporating β‐cyclodextrin/poly(2‐hydroxypropyl acrylate‐co‐N‐vinylimidazole) (CD/poly(HPA‐co‐VI)) with methacrylated gelatin (GelMA), and serves as a scaffold for colloidal crystal arrays. The photonic supraballs derived from the microfluidics techniques, exhibit excellent compatibility with the hydrogel scaffolds, leading to enhanced assembly efficiency. By virtue of hydrogen bonds and host–guest interactions, a series of self‐healable photonic hydrogels (linear, planar, and spiral assemblies) can be facilely assembled. It is demonstrated that the spherical symmetry of the photonic supraballs endows them with identical optical responses independent of viewing angles. In addition, by taking the advantage of angle independent spectrum characteristics, the IPH presents beneficial effects in reflective cooling, which can achieve up to 17.4 °C in passive solar reflective cooling. The strategy represents an easy‐to‐perform platform for the construction of IPH, providing novel insights into macroscopic self‐assembly toward thermal management applications.     

Ordered Arrangement and Optical Properties of Silica‐Stabilized Gold Nanoparticle–PNIPAM Core–Satellite Clusters for Sensitive Raman Detection

Gold–polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal‐enhanced light–matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica‐stabilized gold–poly(N‐isopropylacrylamide) (SiO₂‐Au‐PNIPAM) core–satellite superclusters with a narrow size distribution and their incorporation into ordered self‐organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO₂‐Au‐PNIPAM core–satellite clusters and their application for highly sensitive nanoparticle‐enhanced Raman spectroscopy is demonstrated.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Supramolecular Nanostructures of Chiral Perylene Diimides with Amplified Chirality for High‐Performance Chiroptical Sensing

Chiral supramolecular nanostructures with optoelectronic functions are expected to play a central role in many scientific and technological fields but their practical use remains in its infancy. Here, this paper reports photoconductive chiral organic semiconductors (OSCs) based on perylene diimides with the highest electron mobility among the chiral OSCs and investigates the structure and optoelectronic properties of their homochiral and heterochiral supramolecular assemblies from bottom‐up self‐assembly. Owing to the well‐ordered supramolecular packing, the homochiral nanomaterials exhibit superior charge transport with significantly higher photoresponsivity and dissymmetry factor compared with those of their thin film and monomeric equivalents, which enables highly selective detection of circularly polarized light, for the first time, in visible spectral range. Interestingly, the heterochiral nanostructures assembled from co‐self‐assembly of racemic mixtures show extraordinary chiral self‐discrimination phenomenon, where opposite enantiomeric molecules are packed alternately into heterochiral architectures, leading to completely different optoelectrical performances. In addition, the crystal structures of homochiral and heterochiral nanostructures have first been studied by ab initio X‐ray powder diffraction analysis. These findings give insights into the structure–chiroptical property relationships of chiral supramolecular self‐assemblies and demonstrate the feasibility of supramolecular chirality for high‐performance chiroptical sensing.     

Self‐Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals

Self‐standing nanostructures are of fundamental interest in materials science and nanoscience and are widely used in (opto‐)electronic and photonic devices as well as in micro‐electromechanical systems. To date, large‐area and self‐standing nanoelectrode arrays assembled on flexible substrates have not been reported. Here the fabrication of a hollow nanomesh scaffold on glass and plastic substrates with a large surface area over 1 mm² and ultralow leakage current density (≈1–10 pA mm^?2 @ 2 V) across the empty scaffold is demonstrated. Thanks to the continuous sub‐micrometer space formed in between the nanomesh and the bottom electrode, highly crystalline and dendritic domains of 6,13‐bis(triisopropylsilylethinyl)pentacene growing within the hollow cavity can be observed. The high degree of order at the supramolecular level leads to efficient charge and exciton transport; the photovoltaic detector supported on flexible polyethylene terephthalate substrates exhibits an ultrafast photoresponse time as short as 8 ns and a signal‐to‐noise ratio approaching 10⁵. Such a hollow scaffold holds great potential as a novel device architecture toward flexible (opto‐)electronic applications based on self‐assembled micro/nanocrystals.     

Efficient Aggregation‐Induced Emission Manipulated by Polymer Host Materials

Linear copolymer hosts bearing a number of pillar[5]arene dangling side chains are synthesized for the facile construction of highly emissive supramolecular polymer networks (SPNs) upon noncovalently cross‐linking with a series of tetraphenyethylene (TPE)‐based tetratopic guests terminated with different functional groups through supramolecular host–guest interactions. An extremely high fluorescence quantum yield (98.22%) of the SPNs materials is obtained in tetrahydrofuran (THF) by fine‐tuning the parameters, and meanwhile supramolecular light‐harvesting systems based on spherical supramolecular nanoparticles are constructed by interweaving 9,10‐distyrylanthracene (DSA) and TPE‐based guest molecules of aggregation‐induced emission (AIE) with the copolymer hosts in the mixed solvent of THF/H₂O. The present study not only illustrates the restriction of the intramolecular rotations (RIR)‐ruled emission enhancement mechanism regulated particularly by macrocyclic arene‐containing copolymer hosts, but also suggests a new self‐assembly approach to construct high‐performance light‐harvesting materials.     

Mastering Dendrimer Self‐Assembly for Efficient siRNA Delivery: From Conceptual Design to In Vivo Efficient Gene Silencing

Self‐assembly is a fundamental concept and a powerful approach in molecular science. However, creating functional materials with the desired properties through self‐assembly remains challenging. In this work, through a combination of experimental and computational approaches, the self‐assembly of small amphiphilic dendrons into nanosized supramolecular dendrimer micelles with a degree of structural definition similar to traditional covalent high‐generation dendrimers is reported. It is demonstrated that, with the optimal balance of hydrophobicity and hydrophilicity, one of the self‐assembled nanomicellar systems, totally devoid of toxic side effects, is able to deliver small interfering RNA and achieve effective gene silencing both in cells – including the highly refractory human hematopoietic CD34⁺ stem cells – and in vivo, thus paving the way for future biomedical implementation. This work presents a case study of the concept of generating functional supramolecular dendrimers via self‐assembly. The ability of carefully designed and gauged building blocks to assemble into supramolecular structures opens new perspectives on the design of self‐assembling nanosystems for complex and functional applications.     

Supramolecular Materials via Block Copolymer Self‐Assembly

This review discusses the potential of block copolymer type macromolecular building blocks for the preparation of self‐assembled materials. Three different classes of block copolymer type architectures will be distinguished: (i) coil–coil diblock copolymers, (ii) rod–coil diblock copolymers, and (iii) rod–coil diblock oligomers. The basic principles that underlie the self‐assembly of each of these different building blocks will be discussed. These theoretical considerations are complemented with examples from recent literature that illustrate the potential of the different types of block copolymers to prepare (functional) supramolecular materials. Finally, several strategies will be presented that could allow the preparation of stimuli‐sensitive self‐assembled materials, i.e., materials whose properties can be reversibly manipulated under the action of appropriate external stimuli.     

Concentration‐Controlled Reversible Phase Transitions in Self‐Assembled Monolayers on HOPG Surfaces

Rational control of molecular ordering on surfaces and interfaces is vital in supramolecular chemistry and nanoscience. Here, a systematic scanning tunneling microscopy (STM) study for controlling the self‐assembly behavior of alkoxylated benzene (B‐OC_n) molecules on a HOPG surface is presented. Three different phases have been observed and, of great importance, they can transform to each other by modifying the solute concentration. Further studies, particularly in situ diluting and concentrating experiments, demonstrate that the transitions among the three phases are highly controllable and reversible, and are driven thermodynamically. In addition, it is found that concentration‐controlled reversible phase transitions are general for different chain lengths of B‐OC_n molecules. Such controllable and reversible phase transitions may have potential applications in the building of desirable functional organic thin films and provide a new understanding in thermodynamically driven self‐assembly of organic molecules on surfaces and interfaces.     

Self‐Assembly of Enzyme‐Like Nanofibrous G‐Molecular Hydrogel for Printed Flexible Electrochemical Sensors

Conducting hydrogels provide great potential for creating designer shape‐morphing architectures for biomedical applications owing to their unique solid–liquid interface and ease of processability. Here, a novel nanofibrous hydrogel with significant enzyme‐like activity that can be used as “ink” to print flexible electrochemical devices is developed. The nanofibrous hydrogel is self‐assembled from guanosine (G) and KB(OH)₄ with simultaneous incorporation of hemin into the G‐quartet scaffold, giving rise to significant enzyme‐like activity. The rapid switching between the sol and gel states responsive to shear stress enables free‐form fabrication of different patterns. Furthermore, the replication of the G‐quartet wires into a conductive matrix by in situ catalytic deposition of polyaniline on nanofibers is demonstrated, which can be directly printed into a flexible electrochemical electrode. By loading glucose oxidase into this novel hydrogel, a flexible glucose biosensor is developed. This study sheds new light on developing artificial enzymes with new functionalities and on fabrication of flexible bioelectronics.     

N‐Type Superconductivity in an Organic Mott Insulator Induced by Light‐Driven Electron‐Doping

The presence of interface dipoles in self‐assembled monolayers (SAMs) gives rise to electric‐field effects at the device interfaces. SAMs of spiropyran derivatives can be used as photoactive interface dipole layer in field‐effect transistors because the photochromism of spiropyrans involves a large dipole moment switching. Recently, light‐induced p‐type superconductivity in an organic Mott insulator, κ‐(BEDT‐TTF)₂Cu[N(CN)₂]Br (κ‐Br: BEDT‐TTF = bis(ethylenedithio)tetrathiafulvalene) has been realized, thanks to the hole carriers induced by significant interface dipole variation in the spiropyran‐SAM. This report explores the converse situation by designing a new type of spiropyran monolayer in which light‐induced electron‐doping into κ‐Br and accompanying n‐type superconducting transition have been observed. These results open new possibilities for novel electronics utilizing a photoactive SAMs, which can design not only the magnitude but also the direction of photoinduced electric‐fields at the device interfaces.     

Bionanosphere Lithography via Hierarchical Peptide Self‐Assembly of Aromatic Triphenylalanine

A nanolithographic approach based on hierarchical peptide self‐assembly is presented. An aromatic peptide of N‐(t‐Boc)‐terminated triphenylalanine is designed from a structural motif for the β‐amyloid associated with Alzheimer's disease. This peptide adopts a turnlike conformation with three phenyl rings oriented outward, which mediate intermolecular π–π stacking interactions and eventually facilitate highly crystalline bionanosphere assembly with both thermal and chemical stability. The self‐assembled bionanospheres spontaneously pack into a hexagonal monolayer at the evaporating solvent edge, constituting evaporation‐induced hierarchical self‐assembly. Metal nanoparticle arrays or embossed Si nanoposts could be successfully created from the hexagonal bionanosphere array masks in conjunction with a conventional metal‐evaporation or etching process. Our approach represents a bionanofabrication concept that biomolecular self‐assembly is hierarchically directed to establish a straightforward nanolithography compatible with conventional device‐fabrication processes.