Tibor Kudernac

Electrically driven directional motion of a four-wheeled molecule on a metal surface

Propelling single molecules in a controlled manner along an unmodified surface remains extremely challenging because it requires molecules that can use light, chemical or electrical energy to modulate their interaction with the surface in a way that generates motion. Nature’s motor proteins have mastered the art of converting conformational changes into directed motion, and have inspired the design of artificial systems such as DNA walkers and light- and redox-driven molecular motors. But although controlled movement of single molecules along a surface has been reported, the molecules in these examples act as passive elements that either diffuse along a preferential direction with equal probability for forward and backward movement or are dragged by an STM tip. Here we present a molecule with four functional units—our previously reported rotary motors—that undergo continuous and defined conformational changes upon sequential electronic and vibrational excitation. Scanning tunnelling microscopy confirms that activation of the conformational changes of the rotors through inelastic electron tunnelling propels the molecule unidirectionally across a Cu(111) surface. The system can be adapted to follow either linear or random surface trajectories or to remain stationary, by tuning the chirality of the individual motor units. Our design provides a starting point for the exploration of more sophisticated molecular mechanical systems with directionally controlled motion.

Conversion of light into macroscopic helical motion

A key goal of nanotechnology is the development of artificial machines capable of converting molecular movement into macroscopic work. Although conversion of light into shape changes has been reported and compared to artificial muscles, real applications require work against an external load. Here, we describe the design, synthesis and operation of spring-like materials capable of converting light energy into mechanical work at the macroscopic scale. These versatile materials consist of molecular switches embedded in liquid-crystalline polymer springs. In these springs, molecular movement is converted and amplified into controlled and reversible twisting motions. The springs display complex motion, which includes winding, unwinding and helix inversion, as dictated by their initial shape. Importantly, they can produce work by moving a macroscopic object and mimicking mechanical movements, such as those used by plant tendrils to help the plant access sunlight. These functional materials have potential applications in micromechanical systems, soft robotics and artificial muscles.

Light-Controlled Conductance Switching of Ordered Metal-Molecule-Metal Devices

We demonstrate reversible, light-controlled conductance switching of molecular devices based on photochromic diarylethene molecules. These devices consist of ordered, two-dimensional lattices of gold nanoparticles, in which neighboring particles are bridged by switchable molecules. We independently confirm that reversible isomerization of the diarylethenes employed is at the heart of the room-temperature conductance switching. For this, we take full advantage of the possibility to use optical spectroscopy to follow molecular switching in these samples.

Synthesis and Controlled Self-Assembly of Covalently Linked Hexa-peri-hexabenzocoronene/Perylene Diimide Dyads as Models To Study Fundamental Energy and Electron Transfer Processes

We report the synthesis and photophysical characterization of a series of hexa-peri-hexabenzocoronene (HBC)/perylenetetracarboxy diimide (PDI) dyads that are covalently linked with a rigid bridge. Both the ratio of the two components and the conjugation of the bridging element are systematically modified to study the influence on self-assembly and energy and electron transfer between electron donor HBC and acceptor PDI. STM and 2D-WAXS experiments reveal that both in solution and in bulk solid state the dyads assemble into well-ordered two-dimensional supramolecular structures with controllable mutual orientations and distances between donor and acceptor at a nanoscopic scale. Depending on the symmetry of the dyads, either columns with nanosegregated stacks of HBC and PDI or interdigitating networks with alternating HBC and PDI moieties are observed. UV-vis, photoluminescence, transient photoluminescence, and transient absorption spectroscopy confirm that after photoexcitation of the donor HBC a photoinduced electron transfer between HBC and PDI can only compete with the dominant Förster resonance energy transfer, if facilitated by an intimate stacking of HBC and PDI with sufficient orbital overlap. However, while the alternating stacks allow efficient electron transfer, only the nanosegregated stacks provide charge transport channels in bulk state that are a prerequisite for application as active components in thin film electronic devices. These results have important implications for the further design of functional donor-acceptor dyads, being promising materials for organic bulk heterojunction solar cells and field-effect transistors.

Emerging Solvent‐Induced Homochirality by the Confinement of Achiral Molecules Against a Solid Surface

The unique handedness of chiral molecules affects chemical, physical, and biological phenomena. While observed in solution for helical polymers and self-assembled stacks of molecules, transmission of chiral information is particularly selective at ordered interfaces as a result of geometrical restrictions introduced by two-dimensional (2D) confinement. Chiral amplification of enantiomerically enriched mixtures has been demonstrated either by chemical reactions at the air–water interface, or upon self-assembly on solid surfaces. Homochirality in achiral enantiomorphous monolayers can be realized by merging chiral modifiers in the monolayer or by exposing monolayers to magnetic fields. Alternatively, the potential role of solvents in amplification of chirality and emergence of homochirality at surfaces remains unexplored to date. Herein we show how solvent-induced macroscopic chirality emerges within self-assemblies of achiral molecules on achiral surfaces. It is an exclusive surface-confined process, and as such it differs from “chiral-solvent-” or “chiral-guestinduced” chirality of supramolecular systems in solution. To demonstrate that homochirality emerges at the interface between a chiral liquid and the surface of highly oriented pyrolytic graphite (HOPG), we selected a hydrogen-bonding achiral diamino triazine oligo-(p-phenylenevinylene) oligomer (A-OPV4T, Figure 1). The chiral analogue, ((S)-OPV4T, Figure 1), was recently shown to assemble exclusively in a counter-clockwise (CCW) hydrogen-bonded rosette motif at the liquid–solid interface, with 1-phenyloctane as the achiral solvent. Molecular homochirality is expressed at the supramolecular level as a result of the 2D packing of the chiral rosette. The chiral solvent in the current study,

Nano-electronic switches

This Highlight reviews recent advances in developing light-controlled molecular switches that can be of use for molecular and organic electronics.

On/Off Photoswitching of the Electropolymerizability of Terthiophenes

In this contribution the polymerization of terthiophene, to form an alkene bridged alpha,alpha-coupled sexithiophene polymer, is controlled by light; i.e. the electropolymerizability of the monomer 1F is switched off and on with UV and visible light, respectively. The system comprises of both bis-terthiophene and photochromic dithienylethene units. The presence of a light-switchable unit allows on-off switching of the electropolymerization of the monomer with light. Furthermore the incorporation of the dithienylethene in the polymer backbone increases dramatically the homogenity of the polymer formed (i.e., only sexithiophene units are formed). The derived films are robust and fully retain electrochromic behavior as has been demonstrated through cyclic voltammetry while spatial control (patterning) is readily achieved by applying simple optical masking techniques.

Large All-Hydrocarbon Spoked Wheels of High Symmetry: Modular Synthesis, Photophysical Properties, and Surface Assembly

In a convergent modular synthesis, a very efficient pathway to shape-persistent molecular spoked wheels has been developed and applied according to the covalent-template concept. The structurally defined two-dimensional (2D) oligo(phenylene-ethynylene-butadiynylene)s (OPEBs) presented here are about 8 nm sized hydrocarbons of high symmetry. 48 alkyl chains attached to the molecular plane (hexyl and hexadecyl, respectively) guarantee a high solubility of the compounds. The structure and uniformity of these defined, stable, D(6h) symmetrical compounds is verified by MALDI-MS, GPC analysis, and high-temperature (HT) (1)H and (13)C NMR. Detailed photophysical measurements of nonaggregated molecules in solution (as confirmed by dynamic light scattering (DLS)) focus on the identification of chromophores by comparison with suitable model compounds. Moreover, time-resolved measurements including fluorescence lifetime and depolarization support the chromophore assignment and reveal the occurrence of intramolecular energy transfer. Scanning tunneling microscope (STM) characterization at the solid/liquid interface demonstrates the efficient self-assembly of the OPEBs into hexagonal 2D crystalline layers with a periodicity determined by both the size of the OPEB backbone and the length of peripheral side chains. Atomic force microscope (AFM) studies show a very different assembly behavior of the two spoked wheel molecules, on both graphite and mica. While the hexyl-substituted wheel can form stacked superstructures, hexadecyl groups prevent any ordering in the film aside from the monolayer directly in contact with the surface.

Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches

Diarylethene photochromic switches use light to drive structural changes through reversible electrocyclization reactions. High efficiency in dynamic photoswitching is a prerequisite for applications, as is thermal stability and the selective addressability of both isomers ring-opened and -closed diarylethenes. These properties can be optimized readily through rational variation in molecular structure. The efficiency with regard to switching as a function of structural variation is much less understood, with the exception of geometric requirements placed on the reacting atoms. Ultimately, increasing the quantum efficiency of photochemical switching in diarylethenes requires a detailed understanding of the excited-state potential energy surface(s) and the mechanisms involved in switching. Through studies of the temperature dependence, photoswitching and theoretical studies demonstrate the occurrence or absence of thermal activation barriers in three constitutional isomers that bear distinct π-conjugated systems. We found that a decrease in the thermal barriers correlates with an increase in switching efficiency. The origin of the barriers is assigned to the decrease in π-conjugation that is concomitant with the progress of the photoreaction. Furthermore, we show that balanced molecular design can minimize the change in the extent of π-conjugation during switching and lead to optimal bidirectional switching efficiencies. Our findings hold implications for future structural design of diarylethene photochromic switches.

Intermolecular repulsion through interfacial attraction: toward engineering of polymorphs.

Understanding the formation of crystalline polymorphs is of importance for various applications of materials science. Polymorphism of Schiff base derivatives has recently attracted considerable attention because of its influence on photochromic and thermochromic properties of their 3D crystals. The present investigation extends the study of Schiff base polymorphism to the molecular level by using a combination of scanning tunneling microscopy at the liquid/solid interface and molecular modeling. It is demonstrated that polymorphism of 4-(dodecyloxy)-N-(4-dodecylphenyl)-2-hydroxybenzaldimine (PHB), a Schiff base substituted by alkyl side chains, can occur in 2D crystals when PHB is adsorbed on a surface that is able to exchange charge with the molecule. In particular, on Au(111), PHB molecules self-organize not only into a columnar packing but also in dimer structures. Theoretical and experimental results demonstrate that the dimer-based structure observed on Au(111) originates from molecule/surface interactions, which in turn modify molecule/molecule interactions. The results highlight that the Au(111) substrate is far from being a passive part of the self-assembled system and plays a crucial role in the morphology of 2D polymorphs.