One-dimensional Superstructures Research Articles

Electrostatic-Driven Self-Assembly of Janus-like Monolayer-Protected Metal Nanoclusters.

The generation of controlled microstructures of functionalized nanoparticles has been a crucial challenge in nanoscience and nanotechnology. Efforts have been made to tune ligand charge states that can affect the aggregation propensity and modulate the self-assembled structures. In this work, we modeled zwitterionic Janus-like monolayer ligand-protected metal nanoclusters (J-MPCs) and studied their self-assembly using atomistic molecular dynamics and on-the-fly probability-based enhanced sampling simulations. The oppositely charged ligand functionalization on two hemispheres of a J-MPC elicits asymmetric solvation, primarily driven by distinctive hydrogen bonding patterns in the ligand-solvent interactions. Electrostatic interactions between the oppositely charged residues in J-MPCs guide the formation of one-dimensional and ring-like self-assembled superstructures with molecular dipoles oriented in specific patterns. The pertinent atomistic insights into the intermolecular interactions governing the self-assembled structures of zwitterionic J-MPCs obtained from this work can be used to design a general strategy to create tunable microstructures of charged MPCs.

One-Dimensionally Arranged Quantum-Dot Superstructures Guided by a Supramolecular Polymer Template.

Colloidal quantum dots (QDs) exhibit important photophysical properties, such as long-range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well-defined superstructures, such as three-dimensional (3D) and two-dimensional (2D) superlattices. However, the construction of one-dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D-arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D-arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self-assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low-polarity solvents, the QDs self-adhered to the SP and self-arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D-arranged QDs by an in-depth analysis of the emission spectra and decay curves.

Fan-like MnV2O6 superstructure for rechargeable aqueous zinc ion batteries

In recent years, vanadate has attracted the attention of researchers for its application in electrode materials due to its high specific capacity and layered crystal structure. Herein, a typical manganese vanadium oxides (MnV2O6) product is efficient synthesis via a simple one-step hydrothermal method at 200 °C for 16 h. The as-prepared MnV2O6 sample is found to be the unique one-dimensional fan-like superstructure consist of several nanorods. From a microcosmic point of view, VO6 octahedra sheets are connected by sharing edges which provides highly-open framework for rapid the intercalation and deintercalation of guest ions Therefore, stable MnV2O6 was prepared and used as a cathode material in aqueous zinc ion batteries, which displayed favorable specific discharge capacity, excellent coulombic efficiency and well cycling performance.

One-dimensional and three-dimensional long-range orientated superstructures of PbSe nanocrystals.

We report the 1D linear, 2D square, 2D honeycomb, and 3D topo-epitaxy long-range superstructures of oriented attached PbSe NCs. In particular, we discovered novel 1D linear and 3D superstructures, which implied different formation mechanisms compared with the PbSe superstructures previously reported. Our study not only demonstrates stronger design capability for oriented-attached PbSe superstructures, but also reveals important information about the interfacial behavior of the PbSe NCs during the self-assembly.

Visualization of Charge-Density-Wave Reconstruction and Electronic Superstructure at the Edge of Correlated Insulator 1T-NbSe2.

Edges of low-dimensional quantum systems have profound effects on both fundamental research and device functionality. Real-space investigation of the microscopic edge structures and understanding the edge-modulated electronic properties are of great essence. Here we report the nanoscale structural reconstruction at the atomically sharp edge of a charge-density-wave (CDW) correlated insulator 1T-NbSe2 and the induced electronic properties. We find the CDW unit cells at the edge of single layer (SL) 1T-NbSe2 evolve from the well-defined CDW order in bulk and spontaneously reconstruct into the quartet along the edge. Moreover, we capture an anomalous electronic superstructure along the edge, the periodicity of which is four times that of ordinary CDW lattice. Our findings provide a way to design the one-dimensional electronic superstructure in 2D quantum materials.

Bi8Te3, the 11-Atom Layer Member of the Tetradymite Homologous Series

Bi8Te3 is a member of the tetradymite homologous series, previously shown to be compositionally and structurally distinct from hedleyite, Bi7Te3, yet inadequately characterized structurally. The phase is identified in a sample from the Hedley district, British Columbia, Canada. Compositions are documented by electron probe microanalysis and structures are directly imaged using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM). Results confirm that Bi8Te3 has an 11-atom layer structure, in which three Bi-Bi pairs are placed adjacent to the five-atom sequence (Te-Bi-Te-Bi-Te). Bi8Te3 has trigonal symmetry (space group R3¯m) with unit cell dimensions of a = ~4.4 Å and c = ~63 Å calculated from measurements on representative electron diffraction patterns. The model is assessed by STEM simulations and EDS mapping, all displaying good agreement with the HAADF STEM imaging. Lattice-scale intergrowths are documented in phases replacing Bi8Te3, accounting for the rarity of this phase in nature. These results support prior predictions of crystal structures in the tetradymite homologous series from theoretical modeling and indicate that other phases are likely to exist for future discovery. Tetradymite homologues are mixed-layer compounds derived as one-dimensional superstructures of a basic rhombohedral sub-cell. Each member of the series has a discrete stoichiometric composition and unique crystal structure.

Stacking of Colloidal CdSe Nanoplatelets into Twisted Ribbon Superstructures: Origin of Twisting and Its Implication in Optical Properties

Relatively large faces of colloidal CdSe nanoplatelets (NPLs) drive the anisotropic nanomaterials into one-dimensional superstructures through stacking of NPLs when solvent evaporates. We observe that the assembly could result in the formation of twisted ribbon superstructures with varying pitch length depending on lateral dimensions of CdSe NPLs. Transmission electron microscopy images and simulated projection reveal that stacked NPLs are distorted. The estimation of the contact area between distorted NPLs suggests that this distortion leads to lower energy of overall nanoribbon superstructures. The average pitch length of superstructures on the lateral dimension of NPLs depends on the dimension of NPLs as it alters the distortion angle of NPLs and thus the rotation angle between NPLs. We investigate the energy transfer between NPLs in the context of the lateral dimension of NPLs and the geometric structure of their superstructures via transient photoluminescence decay measurements. Our analysis on the energy-transfer rate indicates that extinction coefficients, which are determined by lateral dimension of NPLs, are more responsible for the energy-transfer change than the rotation angle between CdSe NPLs within twisted ribbon superstructures. The dependence of the energy-transfer rate on the lateral dimension of NPLs highlights the importance of geometry of individual NPLs in the context of optical properties of NPLs in ensemble.

Sequence-Regulated Supracolloidal Copolymers via Copolymerization-Like Coassembly of Binary Mixtures of Patchy Nanoparticles.

Synthetic copolymers of molecular systems serve as an inspiration for creation of one-dimensional copolymer-like superstructures via coassembly of anisometric nanoparticles. In contrast to the covalent and molecular copolymers, the details of formation mechanisms of copolymer-like superstructures, as well as the factors determining their length and the sequences of arranged nanoparticles, are still poorly understood. Herein, we propose a joint theoretical-computational framework to probe into the coassembly mechanism and kinetics of binary mixtures of patchy nanoparticles. By applying the coarse-grained molecular dynamics simulations, it is demonstrated that the coassembly of patchy nanoparticles markedly resembles many aspects of molecular step-growth copolymerization, and the sequences of nanoparticles inside the copolymer-like superstructures can be finely regulated by the relative activity and the initial ingredient of patchy nanoparticles as well as the coassembly strategy. A quantitatively copolymerization-like model is developed to account for the coassembly kinetics of patchy nanoparticles and the sequence distribution of arranged nanoparticles, all governed by the elaborate design of lower-level building units. The jointly theoretical and simulated studies offer mechanistic insights into the copolymerization-like kinetics and the sequence prediction for the coassembly of binary mixtures of patchy nanoparticles, paving the way toward the rational design of copolymer-like superstructures with various sequences and functionalities.

Polymerization-like kinetics of the self-assembly of colloidal nanoparticles into supracolloidal polymers.

The self-assembly of colloidal nanoparticles is conceptually analogous to the polymerization of reactive monomers in molecular systems. However, less is known about the polymerization of colloidal nanoparticles into supracolloidal polymers. Herein, using coarse-grained molecular dynamics and theoretical analysis, we reveal the self-assembly mechanism and kinetics of colloidal nanoparticles constructed from triblock terpolymers. The results show that the formation pathway of supracolloidal polymers involves monomer condensation and oligomer coalescence through the manner of end-to-end collisions. In contrast to the polymerization kinetics of molecular systems, the simulations and theoretical analysis definitely demonstrate that the growth of supracolloidal polymers obeys diffusion-controlled step-growth polymerization kinetics with a variable rate coefficient, where the growth rate is dependent upon the concentration of colloidal nanoparticles and the molecular information of triblock terpolymers. Our findings possess wide implications for understanding the growth of supracolloidal polymers, which is important for the rational and precise design of one-dimensional self-assembled superstructures with new horizons for biomedical applications.

Programmed Coassembly of One-Dimensional Binary Superstructures by Liquid Soft Confinement.

Precise control of particles co-assembly has attracted great attention for fabricating intricate structures and functional materials. However, achieving precise co-assembly of one-dimensional (1D) binary superstructures remains challenging due to the constrained thermodynamic stability and lack of general strategies to control the 1D ordered arrangement of mixed particles. Here, we propose a facile strategy to achieve programmed co-assembly of 1D binary superstructures by liquid soft confinement without particle modification or external field. It reveals that binary particles undergo stepwise confinement and programmed co-assembly in the gradually shrinking and spatially tunable liquid soft confinement. Through tuning the liquid confined space and particles composition, diverse 1D binary superstructures with precisely controlled periodicity, orientation and symmetry are achieved, which shows generality for various particles of different sizes and materials. This work provides a promising route to refined patterning and manufacturing complex materials.

Heteroatom-Doped Perihexacene from a Double Helicene Precursor: On-Surface Synthesis and Properties

We report on the surface-assisted synthesis and spectroscopic characterization of the hitherto longest periacene analogue with oxygen-boron-oxygen (OBO) segments along the zigzag edges, that is, a heteroatom-doped perihexacene 1. Surface-catalyzed cyclodehydrogenation successfully transformed the double helicene precursor 2, i.e., 12a,26a-dibora-12,13,26,27-tetraoxa-benzo[1,2,3-hi:4,5,6-h'i']dihexacene, into the planar perihexacene analogue 1, which was visualized by scanning tunneling microscopy and noncontact atomic force microscopy. X-ray photoelectron spectroscopy, Raman spectroscopy, together with theoretical modeling, on both precursor 2 and product 1, provided further insights into the cyclodehydrogenation process. Moreover, the nonplanar precursor 2 underwent a conformational change upon adsorption on surfaces, and one-dimensional self-assembled superstructures were observed for both 2 and 1 due to the presence of OBO units along the zigzag edges.

Size-Dependent Structure Relations between Nanotubes and Encapsulated Nanocrystals.

The structural organization of compounds in a confined space of nanometer-scale cavities is of fundamental importance for understanding the basic principles for atomic structure design at the nanolevel. Here, we explore size-dependent structure relations between one-dimensional PbTe nanocrystals and carbon nanotube containers in the diameter range of 2.0-1.25 nm using high-resolution transmission electron microscopy and ab initio calculations. Upon decrease of the confining volume, one-dimensional crystals reveal gradual thinning, with the structure being cut from the bulk in either a <110> or a <100> growth direction until a certain limit of ∼1.3 nm. This corresponds to the situation when a stoichiometric (uncharged) crystal does not fit into the cavity dimensions. As a result of the in-tube charge compensation, one-dimensional superstructures with nanometer-scale atomic density modulations are formed by a periodic addition of peripheral extra atoms to the main motif. Structural changes in the crystallographic configuration of the composites entail the redistribution of charge density on single-walled carbon nanotube walls and the possible appearance of the electron density wave. The variation of the potential attains 0.4 eV, corresponding to charge density fluctuations of 0.14 e/atom.

Charge and spin transport in an organic molecular square.

Understanding electronic communication among multiple chromophoric and redox units requires construction of well-defined molecular architectures. Herein, we report the modular synthesis of a shape-persistent chiral organic square composed of four naphthalene-1,8:4,5-bis(dicarboximide) (NDI) sides and four trans-1,2-cyclohexanediamine corners. Single crystal X-ray diffraction reveals some distortion of the cyclohexane chair conformation in the solid state. Analysis of the packing of the molecular squares reveals the formation of highly ordered, one-dimensional tubular superstructures, held together by means of multiple [CH⋅⋅⋅OC] hydrogen-bonding interactions. Steady-state and time-resolved electronic spectroscopies show strong excited-state interactions in both the singlet and triplet manifolds. Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopies on the monoreduced state reveal electron sharing between all four NDI subunits comprising the molecular square.

Water-Mediated Assembly of Gold Nanoparticles into Aligned One-Dimensional Superstructures.

This Article shows that water in ethanol colloids of gold nanoparticles enhances the formation of linear clusters and, more important for applications in electronics, determines their assembly on surfaces. We show by dynamic light scattering that ethanol colloids contain mainly monomers and dimers and that wormlike superstructures are mostly absent, despite UV-vis evidence of aggregation. Water added to the colloid as a cosolvent was found to enhance the number of clusters as well as their average size, confirming its role in linear self-assembly, on the scale of a few particles. Water adsorbed from the atmosphere during coating was also found to be a powerful lever to tune self-assembly on surfaces. By varying the relative humidity, a sharp transition from branched to linear superstructures was observed, showing the importance of water as a cosolvent in the formation of cluster superstructures. We show that one-dimensional superstructures may form due to long-range mobility of precursor clusters on wet surfaces, allowing their rearrangement. The understanding of the phenomenon allows us to statistically align both clusters and resulting superstructures on patterned substrates, opening the way to rapid screening in molecular electronics.

Light-directing chiral liquid crystal nanostructures: from 1D to 3D.

Endowing external, remote, and dynamic control to self-organized superstructures with desired functionalities is a principal driving force in the bottom-up nanofabrication of molecular devices. Light-driven chiral molecular switches or motors in liquid crystal (LC) media capable of self-organizing into optically tunable one-dimensional (1D) and three-dimensional (3D) superstructures represent such an elegant system. As a consequence, photoresponsive cholesteric LCs (CLCs), i.e., self-organized 1D helical superstructures, and LC blue phases (BPs), i.e., self-organized 3D periodic cubic lattices, are emerging as a new generation of multifunctional supramolecular 1D and 3D photonic materials in their own right because of their fundamental academic interest and technological significance. These smart stimuli-responsive materials can be facilely fabricated from achiral LC hosts by the addition of a small amount of a light-driven chiral molecular switch or motor. The photoresponsiveness of these materials is a result of both molecular interaction and geometry changes in the chiral molecular switch upon light irradiation. The doped photoresponsive CLCs undergo light-driven pitch modulation and/or helix inversion, which has many applications in color filters, polarizers, all-optical displays, optical lasers, sensors, energy-saving smart devices, and so on. Recently, we have conceptualized and rationally synthesized different light-driven chiral molecular switches that have very high helical twisting powers (HTPs) and exhibit large changes in HTP in different states, thereby enabling wide phototunability of the systems by the addition of very small amounts of the molecular switches into commercially available achiral LCs. The light-driven chiral molecular switches are based on well-recognized azobenzene, dithienylcyclopentene, and spirooxazine derivatives. We have demonstrated high-resolution and lightweight photoaddressable displays without patterned electronics on flexible substrates. The wide tunability of the HTP furnishes reflection colors encompassing the whole visible spectrum and beyond in a reversible manner. Photomodulation of the helical pitch of the CLCs has been achieved by UV, visible, and near-infrared (NIR) light irradiation. NIR-light-induced red, green, and blue (RGB) reflections have been leveraged only by varying the power density of the IR laser. Some chiral switches are found to confer helix inversion to the cholesteric systems, which qualifies the CLCs for applications where circularly polarized light is involved. Dynamic and static primary RGB reflection colors have been achieved in a single film. LC BPs have been fabricated and investigated in the context of self-organized 3D photonic band gap (PBG) materials, and dynamic phototuning of the PBG over the visible region has been achieved. Omnidirectional lasing and tuning of the laser emission wavelength have also been attained in monodisperse photoresponsive CLC microshells fabricated by a capillary-based microfluidic technique. This Account covers the research and development in our laboratory starting from the design concepts and synthesis of photodynamic chiral molecular switches to their applications in the fabrication of photoresponsive CLCs and BPs. Potential and demonstrated practical applications of photoresponsive CLCs, microshells, and BPs are discussed, and the Account concludes with a brief forecast of what lies beyond the horizon in this rapidly expanding and fascinating field.

Anisotropic electronic conduction in metal nanofilms grown on a one-dimensional surface superstructure

We performed in situ conductivity measurements by multiple microscopic probes of Ag nanofilms grown on a periodic array of indium atomic wires on Si(111). Within the investigated thickness range the transport properties differ markedly from the bulk case. The ratio between the in-plane conductivity along and perpendicular to the In wires is 1.4 for the 3 monolayer (0.7 nm) thick Ag film and approaches unity with increasing film thickness. The observed anisotropy at the initial stage of the film growth is far larger than expected from the quasi-one-dimensional quantum well electronic structure of the films and ascribed to the carrier scattering at the film/vacuum and film/substrate interfaces. Our findings show that an ordered monolayer inserted at the interface enables drastic changes of the transport behavior of the whole metal nanofilm.

Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale.

The assembly of metal ions with organic ligands through the formation of coordination bonds gives crystalline framework materials, known as metal-organic frameworks (MOFs), which recently emerged as a new class of porous materials. Besides the structural designability of MOFs at the molecular length scale, the researchers in this field very recently made important advances in creating more complex architectures at the mesoscopic/macroscopic scale, in which MOF nanocrystals are used as building units to construct higher-order superstructures. The structuring of MOFs in such a hierarchical order certainly opens a new opportunity to improve the material performance via design of the physical form rather than altering the chemical component. This review highlights these superstructures and their applications by categorizing them into four dimensionalities, zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) superstructures. Because the key issue for structuring of MOFs is to spatially control the nucleation process in desired locations, this review conceptually categorizes the available synthetic methodologies from the viewpoint of the reaction system.

Atomic ordering in Au-(42 to 50) at.%Pd: A diffuse scattering and first-principles investigation

Atomic ordering in Au-Pd alloys was studied by diffuse x-ray scattering and first-principles methods. Diffuse scattering was done of a single crystal of Au-48 at.% Pd that was aged at 703 K for 24 days. The weakly modulated short-range-order scattering exhibits diffuse maxima with an incommensurate wave vector, which can be related to a Fermi-surface nesting mechanism. From effective pair interaction parameters determined by the inverse Monte Carlo method, a one-dimensional long-period superstructure of the CH structure, LPS1, was found for AuPd. Concurrent electronic-structure calculations of the effective cluster interaction (ECI) parameters indicated the presence of another closely related superstructure, LPS2, at 0 K. At the same time, direct first-principles calculations of the total energies of the CH structure and further one-dimensional long-period superstructures predicted the stabilization of LPS4. Although the energy differences between these structures are small and a complex behavior of the effective interactions is expected due to the Fermi-surface nesting, experimental data and theoretical results both support the stabilization of a long-period superstructure of the CH structure for AuPd at 0 K. The ECI parameters determined by the screened generalized perturbation method also predicted a ground-state structure different from Au${}_{7}$Pd${}_{5}$, previously obtained from cluster expansion calculations. Its energetic preference was confirmed by direct total-energy calculations.

A One-Dimensional Superstructure from the Self-Assembly of Ag Nanoparticles Induced by Cu2+ Ion Coordination

The self-assembly of spherical silver nanoparticles with variable size and controlled organization using triglycine as an organic template is described. Triglycine and silver nitrate were used as the starting materials for the preparation of the spherical nanoparticles, and in the presence of copper cations, the particles further self-assembled into one dimensional nanostructures. The formation of supramolecular nanoaggregates was evaluated by means of UV/vis, TEM, SEM, and energy dispersive X-ray spectroscopy.

オクタデヒドロジベンゾ[12]アヌレンのパイスタックカラム超構造における積層方向の制御

オクタデヒドロジベンゾ[12]アヌレンのパイスタックカラム超構造における積層方向の制御