Dynamically switchable supramolecular systems offer exciting possibilities in building smart surfaces, the structure and thus the function of which can be controlled by using external stimuli. Here we demonstrate an elegant approach where the guest binding ability of a supramolecular surface can be controlled by inducing structural transitions in it. A physisorbed self-assembled network of a simple hydrogen bonding building block is used as a switching platform. We illustrate that the reversible transition between porous and nonporous networks can be accomplished using an electric field or applying a thermal stimulus. These transitions are used to achieve controlled guest release or capture at the solution-solid interface. The electric field and the temperature-mediated methods of guest release are operative at different length scales. While the former triggers the transition and thus guest release at the nanometer scale, the latter is effective over a much larger scale. The flexibility associated with physisorbed self-assembled networks renders this approach an attractive alternative to conventional switchable systems.

A new class of polymers, which have a double-stranded polybinorbornene skeleton with multilayer planar oligoaryl linkers, defined as polymeric ladderphanes, are synthesized. The structures of these ladderphanes are determined by spectroscopic means. Photophysical studies and time-resolved fluorescence spectroscopic investigations reveal that there is a strong interaction between the chromophore linkers. Thus, Soret band splitting in the absorption spectrum of the polymer with porphyrin linker (12e), significant fluorescence quenching with oligoaryl linkers (12b-d), and excimer emission with a terphenylene-diethynylene linker (12a) are characteristic photophysical properties of these polymers. Scanning tunneling microscopy shows that polymers 12b and d exhibit a ladder-like morphology and form a supramolecular assembly leading to a two-dimensional ordered array on a highly oriented pyrolytic graphite surface.

Long and planar: Facile syntheses of soluble hexarylene diimides (HDI) and octarylene diimides (ODI) are described. They are stable in both solution and the solid state and exhibit broad and intense NIR absorption. Scanning tunneling microscopy (STM) reveals that HDI, after deposition from solution, forms a unique herringbone bilayer or stable multilayers depending on the concentration.

The control of spatial arrangements of molecular building blocks on surfaces opens the foundational step of the bottom-up approach toward future nanotechnologies. Contemporarily, the domain size of monolayers exhibiting crystallinity falls in the submicrometer scale. Developed herein is a method that allows the alignment of polyaromatics with one-single domain for as long as 7 mm. Even more exciting is the fact that the method is applicable to every laboratory and costs practically nothing. The monolayers are prepared simply by placing a piece of folded lens paper against the substrate and the deposition solution containing the compound of interest. The preparation scheme is similar to the Couette flow where the laminar flow takes place between two concentric walls, one of which rotates and creates viscous drag proven useful to align macromolecules. The method can induce an edge-on orientation for 3,6,11,14-tetradodecyloxydibenzo[g,p]chrysene (DBC-OC12), 3,6,12,15-tetrakis(dodecyloxy)tetrabenz[a,c,h,j]anthracene (TBA-OC12), and hexakis(4-dodecyl)-peri-hexabenzocoronene (HBC-C12) and unsubstituted coronene which would otherwise adopt the face-on arrangement on graphite. This finding will be useful to the research and industry that demands high quality alignment of polyaromatics such as OTFTs, optical polarizers, and nanodevices associated with molecular self-assembly.

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Nanostructured molecular thin films adsorbed on solid surfaces form the basis of numerous applications. Long-range order within adsorbed molecules is very often a desirable property for such systems. In this contribution, we report a simple and efficient method to fabricate well-aligned thin films of organic molecules over a few millimeter squares. The strategy involves use of capillary force in a two-step flow method to induce large-area alignment of multilayers of molecules at the organic liquid-solid interface. Furthermore, we also demonstrate the influence of alignment on the electron transport through these well-aligned thin films using scanning tunneling spectroscopy.

The oriented external electric field of a scanning tunneling microscope (STM) has recently been adapted for controlling the chemical reaction and supramolecular phase transition at surfaces with molecular precision.

Using trimesic acid (TMA) as a model system by means of scanning tunneling microscope (STM) equipped with a temperature controller, here, we report a temperature-assisted method to cooperatively control electric-field-induced supramolecular phase transitions at the liquid/solid interface. Octanoic acid is used as a solvent due to its good solubility for TMA and its less complicated pattern formed under negative STM bias (e.g., only chicken-wire polymorphs existing). At positive substrate bias, STM revealed that TMA assembly based on temperature modulations underwent phase transitions from a porous (22 °C) to a flower (45 °C) and further to a zigzag (68 °C) structure. The transitions are ascribed to the partial deprotonation of the carboxyl groups of TMA. Both the temperature and electrical polarity of the substrate are crucial, i.e., the transitions only take place at positive substrate bias and elevated temperatures. Molecular mechanics simulations were carried out to calculate the temperature and electric field dependence of the adsorption enthalpy and free energy of the chicken-wire assembly of TMA on the two layers of graphene surface. The calculated decrease in adsorption enthalpy with the increase of temperature and electric field values that causes the TMA chicken-wire assembly to be less stable is proposed to promote the occurrence of the phase transition observed by STM. This study paves the way toward program-controlled supramolecular phase switching via the synergic effect of electrical and thermal stimuli.