The creation of ordered nanoparticle assemblies is one of the main prerequisites for the utilization of nanoparticles in advanced device applications. However, while considerable progress has been made in the precision synthesis of high quality, uniform nanoparticles of different compositions, sizes and shapes, our ability to organize them into ordered structures still faces major challenges. This Feature Article focuses on a facile approach developed in recent years for the fabrication of two-dimensionally organized nanoparticle assemblies, which is based on patterning as a simple and straightforward assembly mechanism and on block copolymer films as easily created templates.

Super bowl: Bicorannulenyl, a large biaryl composed of two corannulene bowls, effectively becomes an overcrowded ethylene upon reduction to form a dianion (see picture). DFT calculations and NMR spectroscopic experiments reveal the double-bond character of the connection between the two bowls. Three stable diastereomers that interconvert through bowl inversions and central bond rotations were shown to exist.

The supramolecular dimerization of tetraanionic corannulene is utilized as a self-assembly motif for the construction of highly charged, buckybowl-based supramolecular oligomers. Oligomers of up to 7 units (3900 g mol(-1)) of reduced dicorannulenic monomers are identified and characterized by various NMR techniques, and the reversibility of their assembly is established through the concentration dependence of their molecular weight and the effect of monofunctional chain-stoppers.

We present a facile route for the fabrication of hierarchical, hyper-branched nanoparticle superstructures guided by a two-dimensional polymer template. Our approach utilises semi-crystalline poly(ethylene glycol) (PEG) films featuring branched arrays of channels as templates for the patterning of gold nanoparticles of different sizes and surface chemistry. The deposited nanoparticles preferentially adhere to the channel edges, forming nanoparticle chains decorating the contours of the surface topography. This preference is shown to be independent of nanoparticle size and surface chemistry; however, smaller nanoparticles appear to be more sensitive to subtle topographical attributes of the film. Additionally, the ability to induce the dissolution of the crystalline polymer domains during the nanoparticle patterning process leads to a controlled exchange of these domains with fractal nanoparticle arrays. This dynamic templating methodology adds another dimension to the toolbox of existing patterning methodologies.

This tutorial review discusses synthetic strategies towards aromatic belts, defined here as double-stranded conjugated macrocycles, such as [n]cyclacenes, [n]cyclophenacenes, Schluter belt, and Vogtle belt. Their appeal stems, firstly, from the unique nature of their conjugation, having p orbitals oriented radially rather than perpendicular to the plane of the macrocycle. Secondly, as aromatic belts are model compounds of carbon nanotubes of different chiralities, a synthetic strategy towards the buildup of structural strain in these compounds could finally open a route towards rational chemical synthesis of carbon nanotubes. The elusiveness of these compounds has stimulated fascinating and ingenious synthetic strategies over the last decades. The various strategies are classified here by their approach to the buildup of structural strain, which is the main obstacle in the preparation of these curved polyarenes.

Two-dimensional, hierarchical assemblies of nanorods were obtained by exploiting the structures afforded by block copolymers in ultrathin films. Under the appropriate conditions, the nanorods segregate to the film surface already upon casting the composite film, and organize with the block copolymer through phase separation. In this paper we compare the structures formed by CdSe nanorods of three different lengths and two polystyrene-block-poly(methyl methacrylate) copolymers with different nanorods/copolymer ratios, and study the temporal evolution of the structure in each case. It is found that the initial morphology of the film largely dictates the resulting structure. The combination of short nanorods and/or short copolymers is shown to be more prone to morphological defects, while assembling long nanorods with long copolymers leads to highly organized nanorod morphologies. These phenomena are explained by a combination of kinetic and thermodynamic factors.

Using computer simulation of a coarse-grained model for supramolecular polymers, we investigate the potential of quasiblock copolymers (QBCPs) assembled on chemically patterned substrates for creating device-oriented nanostructures. QBCPs are comprised of AB diblock copolymers and supramolecular B segments that can reversibly bond to any available B terminus, on either the copolymers or the B oligomers, creating a polydisperse blend of B homopolymers, and AB and ABA copolymers. We demonstrate the defect-free replication of patterns with perpendicularly crossing, A-preferential lines, where the same QBCP can simultaneously replicate patterns differing by up to 50% in their length scales. We demonstrate how the pattern affects the distribution of molecular architectures and the key role of supramolecular associations for replicating patterns with different length scales.

Co-assembly of cadmium selenide nanorods in block copolymer films gives rise to anisotropic, hierarchical nanorod superstructures at the film surface. Unlike their observed behavior in the bulk composite, the nanorods preferentially orient perpendicular to the direction of the block copolymer domain, and the number of nanorods assembled across the domain is controlled by the ratio between the nanorod length and the domain width.

We report the design and implementation of a vertical organic field effect transistor which is compatible with standard device fabrication technology and is well described by a self consistent device model. The active semiconductor is a film of C(60) molecules, and the device operation is based on the architecture of the nanopatterned source electrode. The relatively high resolution fabrication process and maintaining the low-cost and simplicity associated with organic electronics, necessitates unconventional fabrication techniques such as soft lithography. Block copolymer self-assembled nanotemplates enable the production of conductive, gridlike metal electrode. The devices reported here exhibit On/Off ratio of 10(4).

Self-assembly of nanoparticles on liquid-metal droplets (see image) provides a simple, effective approach to electronic devices with nanoscale control of the metal/nanoparticle junctions. This approach enables the inexpensive fabrication of a large number of devices and deposition on large-area substrates.

We develop a mesoscopic density functional theory (DFT)-based Monte-Carlo approach for studying the phase behaviour of multi-component systems comprised of irreversibly bonded, conventional macromolecules and supramolecular entities. The latter can reversibly associate with each other and the conventional components to ‘‘living’’, equilibrium polymers. The computational approach can be applied to a broad class of supramolecular systems and we focus here on quasi-block copolymer systems that contain conventional, ‘‘dead’’ AB-copolymers with a supramolecular B-terminus and supramolecular B-units. The simulations show that, by properly selecting the architecture of the ‘‘dead’’ copolymers and by varying the supramolecular association constant and the incompatibility between the segment species, A and B, one obtains a variety of different microphase-separated morphologies and macrophase separations. Two representative phase diagrams are reported as a function of the association constant, E(b), and the Flory-Huggins parameter, chi, quantifying the repulsion between A and B segments. The simulation results are qualitatively rationalised by considering the dependence of the stoichiometry on the system’s parameters, and fractionation effects between coexisting phases are illustrated.

The bicorannulenyl molecule is composed of two chiral bowls tethered by a single bond in a helical fashion. This simple combination of two chiral motifs gives rise to rich dynamic stereochemistry, where 12 conformers interconvert through bowl inversions and central bond rotation, and enantiomerizations occur via multistep processes. Interestingly, 8 out of 10 transition states are chiral, giving rise to mostly chiral enantiomerization pathways, where the molecule changes chirality without passing through an achiral conformation. However, analysis of the stereochemical landscape by DFT calculations and variable temperature NMR spectroscopy reveals that the energetically most favorable enantionterization pathway passes through one of the two achiral transition states. Single-crystal X-ray diffraction corroborates the DFT results and provides information on packing modes of bicorannulenyl molecules in the solid state that have not been seen previously for other buckybowls.

A coarse-grained lattice gas model is developed to study the drying-mediated self-assembly of nanoparticles on diblock copolymer substrates. The model describes the nanoparticles, the solvent and the diblock copolymer on length scales that are typical to the solvent bulk correlation length. Monte Carlo simulation techniques are used to delineate the various mechanisms of this out-of-equilibrium hierarchical self-assembly. Several different assembly scenarios corresponding to different selectivity of the nanoparticles/liquid/substrate are discussed. The role of surface tension, evaporation rate, diffusion rate, nanoparticle, coverage, and diblock copolymer periodicity is explored. Optimal conditions to form a stripe phase of nanoparticles along with predictions of novel 3D structures resulting from high nanoparticle and solvent selectivity are described.

Robust arrays of ordered nanoparticles (see Figure and cover) have been created by combining two self-assembly strategies: microphase separation of block copolymers and coordination chemistry. Thin films of a microphase-separated block copolymer serve as templates for patterning of terpyridine-functionalized gold nanoparticles. Subsequent treatment with iron salts crosslinks the patterned nanoparticles via the formation of iron–terpyridine complexes.

We demonstrate the use of molecular recognition to control the spatial distribution of guest molecules within block copolymer films. Block copolymers bearing recognition units were combined with complementary and noncomplementary molecules, and the extent of segregation of these molecules into the different domain types within microphase-separated thin films was quantitatively analyzed using dynamic secondary ion mass spectrometry (SIMS). Complementarity between the guest molecules and the polymer functionalities proved to be a key factor and an efficient tool for directing the segregation preference of the molecules to the different domain types. The effect of segregation preference on the glass transition temperature was studied using differential scanning calorimetry (DSC), and the results corroborate the SIMS findings. In a complementary study, guests with tunable sizes (via dendron substituents) were used to control block copolymer morphology. Morphological characterization using transmission electron microscopy (TEM) and X-ray diffraction reveal that selectivity differences can be directly translated into the ability to obtain different morphologies from recognition unit-functionalized block copolymer scaffolds.

Nanoparticle-polymer composites are diverse and versatile functional materials, with applications ranging from electronic device fabrication to catalysis. This review focuses on the use of chemical design to control the structural attributes of polymer-mediated assembly of nanoparticles. We will illustrate the use of designed particles and polymers to create nanocomposites featuring interesting and pragmatic structures and properties. We will also describe applications of these engineered materials.

Copolymers consisting of styrene and 4-chloromethylstyrene (CMS) were functionalized via reaction with 9-anthracenecarboxylic acid, providing the corresponding esters. Increasing degrees of functionalization were found to increase the glass transition temperature, influence chain packing density, and induce microphase separation in block copolymer structures. The approach demonstrated in this study facilitates the investigation of the relationship between structure of side-chain groups and polymer properties, providing a general approach for the study of the effect of chemical functionality on material properties of polymers.

The effect of including vs. excluding diffuse functions while calculating numerous parameters of PAH anions by various calculation methods is discussed. The omission of diffuse functions. appears to have a negligible effect while calculating geometry parameters or total energy; thus, acceptable results may be obtained without them. The conclusions for charge density appear to be the same; however, limited results make an unambiguous claim unachievable. Calculating H-1- and C-13-NMR shifts undoubtedly requires the use of these functions.

Polystyrene scaffolds were grafted with model functionalities featuring strongly interacting hydrogen bonding and aromatic stacking elements. Both glass transition temperatures and degree of microphase separation in functionalized block copolymers depend on the nature of the functionality and in particular on the strength of intermolecular interactions. The polymers under study were amorphous; it was found, however, that domain periodicities of functionalized diblock copolymers in the microphase-separated state are extremely sensitive to local interactions between functionalities and can express even subtle differences in interaction strength. The results emphasize the ability to fine-tune polymer microstructure and thermomechanical behavior using supramolecular chemistry.

Nanoparticles provide key tools for bridging the gap between ‘‘bottom-up’’ synthetic methods and ‘‘top-down’’ fabrication. In this Account we describe some of the unique structural aspects of nanoparticles and the use of these attributes to the creation of devices with tunable specificity and environmental response. We also explore the use of nanoparticles as ‘‘building blocks’’ for the creation of nanocomposite materials that feature structural control from the molecular to the micron scale.