Flexible Phenanthracene Nanotubes for Explosive Detection.

Phenanthracene nanotubes with arylene-ethynylene-butadiynylene rims and phenanthracene walls are synthesized in a modular bottom-up approach. One of the rims carries hexadecyloxy side chains, mediating the affinity to highly oriented pyrolytic graphite. Molecular dynamics simulations show that the nanotubes are much more flexible than their structural formulas suggest: In 12, the phenanthracene units act as hinges that flip the two macrocycles relative to each other to one of two possible sites, as quantum mechanical models suggest and scanning tunneling microscopy investigations prove. Unexpectedly, both theory and experiment show for 13 that the three phenanthracene hinges are deflected from the upright position, accompanied by a deformation of both macrocycles from their idealized sturdy macroporous geometry. This flexibility together with their affinity to carbon-rich substrates allows for an efficient host-guest chemistry at the solid/gas interface opening the potential for applications in single-walled carbon nanotube-based sensing, and the applicability to build new sensors for the detection of 2,4,6-trinitrotoluene via nitroaromatic markers is shown.

Nanoscale π-conjugated ladders.

It is challenging to increase the rigidity of a macromolecule while maintaining solubility. Established strategies rely on templating by dendrons, or by encapsulation in macrocycles, and exploit supramolecular arrangements with limited robustness. Covalently bonded structures have entailed intramolecular coupling of units to resemble the structure of an alternating tread ladder with rungs composed of a covalent bond. We introduce a versatile concept of rigidification in which two rigid-rod polymer chains are repeatedly covalently associated along their contour by stiff molecular connectors. This approach yields almost perfect ladder structures with two well-defined π-conjugated rails and discretely spaced nanoscale rungs, easily visualized by scanning tunnelling microscopy. The enhancement of molecular rigidity is confirmed by the fluorescence depolarization dynamics and complemented by molecular-dynamics simulations. The covalent templating of the rods leads to self-rigidification that gives rise to intramolecular electronic coupling, enhancing excitonic coherence. The molecules are characterized by unprecedented excitonic mobility, giving rise to excitonic interactions on length scales exceeding 100 nm. Such interactions lead to deterministic single-photon emission from these giant rigid macromolecules, with potential implications for energy conversion in optoelectronic devices.

Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze.

Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]-phenyl-C61-butyrate, and a perylene monoimide are investigated. All compounds form two-dimensional crystals on highly oriented pyrolytic graphite at the solid-liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar-pillar distances by 15 % and block unspecific intercalation.

Nanopatterns of molecular spoked wheels as giant homologues of benzene tricarboxylic acids.

Molecular spoked wheels with D 3h and C s symmetry are synthesized by Vollhardt trimerization of C 2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D 3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, C s-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing.

Highly Strained Nanoscale Bicyclophane Monolayers Entering the Third Dimension: A Combined Synthetic and Scanning Tunneling Microscopy Investigation.

Invited for this month's cover are the collaborating groups of Prof. Dr. Sigurd Höger and Dr. Stefan-S. Jester from Rheinische Friedrich-Wilhelms-Universität Bonn, Germany. The cover picture shows a bicyclophane that forms a two-dimensional supramolecular nanopattern on graphite at the solid/liquid interface. After adsorption, the central unit points towards the volume phase. Read the full text of the article at 10.1002/cplu.202000711.

Highly Strained Nanoscale Bicyclophane Monolayers Entering the Third Dimension: A Combined Synthetic and Scanning Tunneling Microscopy Investigation.

Tetrabromo aromatics can be synthesized by the Fischer-Zimmermann condensation of appropriate pyrylium salts with arylene dicarboxylic acid salts. Their cyclization by intramolecular Yamamoto coupling yields strained bicyclophanes with adjustable sizes and different intraannular bridges. All compounds adsorb at the solid/liquid interface on highly oriented pyrolytic graphite (HOPG) and are investigated by scanning tunneling microscopy (STM) with submolecular resolution. The observed two-dimensional (2D) supramolecular nanopatterns depend only on the sizes and alkoxy periphery of the cyclophanes and are independent of the specific structures of the intraannular bridges. Since the central arylene moieties of the smaller species are oriented perpendicular to the planes of the bicyclophanes, their substituents protrude from the surface by up to 1.6 nm after adsorption. Therefore, these molecules are attractive platforms for addressing the volume phase above the graphite surface.

Interplay Between J- and H-Type Coupling in Aggregates of π-Conjugated Polymers: A Single-Molecule Perspective.

Strong dipole-dipole coupling within and between π-conjugated segments shifts electronic transitions, and modifies vibronic coupling and excited-state lifetimes. Since J-type coupling between monomers along the conjugated-polymer (CP) chain and H-type coupling of chromophores between chains of a CP compete, a superposition of the spectral modifications arising from each type of coupling emerges, making the two couplings hard to discern in the ensemble. We introduce a single-molecule H-type aggregate of fixed spacing and variable length of up to 10 nm. HJ-type aggregate formation is visualized intuitively in the scatter of single-molecule spectra.

Nanopatterns of arylene-alkynylene squares on graphite: self-sorting and intercalation.

Supramolecular nanopatterns of arylene-alkynylene squares with side chains of different lengths are investigated by scanning tunneling microscopy at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Self-sorting leads to the intermolecular interdigitation of alkoxy side chains of identical length. Voids inside and between the squares are occupied by intercalated solvent molecules, which numbers depend on the sizes and shapes of the nanopores. In addition, planar and non-planar coronoid polycyclic aromatic hydrocarbons (i.e., butyloxy-substituted kekulene and octulene derivatives) are found to be able to intercalate into the intramolecular nanopores.

Supramolecular nanopatterns of H-shaped molecules.

Alkoxy-substituted phenylene-ethynylene-butadiynylenes (PEBs) are connected via 1H-benzimidazole units to form H-shaped molecular scaffolds that self-assemble on graphite at the solid/liquid interface. Spacer lengths and end groups determine supramolecular tiling patterns, as shown via scanning tunneling microscopy (STM).

Donor-acceptor interactions between cyclic trinuclear pyridinate gold(i)-complexes and electron-poor guests: nature and energetics of guest-binding and templating on graphite.

Donor-acceptor-type interactions between π-electron systems are of high relevance in the design of chemical sensors. Due to their electron-rich nature, cyclic trinuclear complexes (CTCs) of gold(i) are ideal receptor sites for electron-deficient aromatic analytes. Scanning tunneling microscopy provided insight into the structures of two-dimensional crystals of pyridinate gold CTCs that form on a graphite template at the solid/liquid interface. One polymorph thereof - in turn - templated the on-top co-adsorption of π-acidic pyrazolate CTCs as electron-poor guests up to a certain threshold. From NMR titration experiments, we quantified free energies of -6.1 to -7.5 kcal mol-1 for the binding between pyridinate gold(i) CTCs and π-acidic pyrazolate CTCs. Quantum chemical calculations revealed that these interactions are largely dominated by London dispersion. These results give a more detailed insight into a rational design of sensitive CNT- or graphene-based sensors for π-acidic analytes, such as electron-deficient aromatics.

A Liquid-Crystalline Phenylene-Based Shape-Persistent Molecular Spoked Wheel.

Molecular spoked wheels with an all-phenylene backbone and different alkoxy side chain substitution patterns were synthesized using a cobalt-catalyzed [2 + 2 + 2] cycloaddition and subsequent template-directed cyclization via Yamamoto coupling. The two-dimensional organization of the molecules at the solid/liquid interface was investigated by means of scanning tunneling microscopy, allowing imaging of the molecular structure with submolecular resolution. With the right proportion of the flexible alkyl corona to the rigid core, mesomorphic behavior of one compound could be observed over a wide temperature range.

Daisy Chain Rotaxanes Made from Interlocked DNA Nanostructures.

We report the stepwise assembly of supramolecular daisy chain rotaxanes (DCR) made of double-stranded DNA: Small dsDNA macrocycles bearing an axle assemble into a pseudo-DCR precursor that was connected to rigid DNA stoppers to form DCR with the macrocycles hybridized to the axles. In presence of release oligodeoxynucleotides (rODNs), the macrocycles are released from their respective hybridization sites on the axles, leading to stable mechanically interlocked DCRs. Besides the expected threaded DCRs, certain amounts of externally hybridized structures were observed, which dissociate into dumbbell structures in presence of rODNs. We show that the genuine DCRs have significantly higher degrees of freedom in their movement along the thread axle than the hybridized DCR precursors. Interlocking of DNA in DCRs might serve as a versatile principle for constructing functional DNA nanostructures where the movement of the subunits is restricted within precisely confined tolerance ranges.

Fast Oxidative Cyclooligomerization towards Low- and High-Symmetry Thiophene Macrocycles.

Macrocycles with quaterthiophene subunits were obtained by cyclooligomerization by direct oxidative coupling of unsubstituted dithiophene moieties. The rings were closed with high selectivity by an α,ß'-connection of the thiophenes as proven by NMR spectroscopy. The reaction of the precursor with terthiophene moieties yielded the symmetric α,α'-linked macrocycle in low yield together with various differently connected isomers. Blocking of the ß-position of the half-rings yielded selectively the α,α'-linked macrocycle. Selected cyclothiophenes were investigated by scanning tunneling microscopy, which displayed the formation of highly ordered 2D crystalline monolayers.

Temporal Fluctuations in Excimer-Like Interactions between π-Conjugated Chromophores.

Inter- or intramolecular coupling processes between chromophores such as excimer formation or H- and J-aggregation are crucial to describing the photophysics of closely packed films of conjugated polymers. Such coupling is highly distance dependent and should be sensitive to both fluctuations in the spacing between chromophores as well as the actual position on the chromophore where the exciton localizes. Single-molecule spectroscopy reveals these intrinsic fluctuations in well-defined bichromophoric model systems of cofacial oligomers. Signatures of interchromophoric interactions in the excited state--spectral red shifting and broadening and a slowing of photoluminescence decay--correlate with each other but scatter strongly between single molecules, implying an extraordinary distribution in coupling strengths. Furthermore, these excimer-like spectral fingerprints vary with time, revealing intrinsic dynamics in the coupling strength within one single dimer molecule, which constitutes the starting point for describing a molecular solid. Such spectral sensitivity to sub-Ångström molecular dynamics could prove complementary to conventional FRET-based molecular rulers.

Exciton Localization in Extended π-Electron Systems: Comparison of Linear and Cyclic Structures.

We employ five π-conjugated model materials of different molecular shape-oligomers and cyclic structures-to investigate the extent of exciton self-trapping and torsional motion of the molecular framework following optical excitation. Our studies combine steady state and transient fluorescence spectroscopy in the ensemble with measurements of polarization anisotropy on single molecules, supported by Monte Carlo simulations. The dimer exhibits a significant spectral red shift within ∼100 ps after photoexcitation which is attributed to torsional relaxation. This relaxation mechanism is inhibited in the structurally rigid macrocyclic analogue. However, both systems show a high degree of exciton localization but with very different consequences: while, in the macrocycle, the exciton localizes randomly on different parts of the ring, scrambling polarization memory, in the dimer, localization leads to a deterministic exciton position with luminescence characteristics of a dipole. Monte Carlo simulations allow us to quantify the structural difference between the emitting and absorbing units of the π-conjugated system in terms of disorder parameters.

A giant molecular spoked wheel.

The modular synthesis of a defined, rigid molecular spoked wheel structure with the sum formula C1878H2682 and a diameter of about 12 nm is described. The attached 96 dodecyl side chains provide the solubility of the 25 260 Da compound in common organic solvents. At the octanoic acid/highly oriented pyrolytic graphite interface, the molecules self-assemble to form an ordered 2D lattice, which is investigated by scanning tunneling microscopy, displaying their structure with submolecular resolution.

Mechanically interlocked DNA nanostructures for functional devices.

CONSPECTUS: Self-assembled functional DNA oligonucleotide based architectures represent highly promising candidates for the creation of nanoscale devices. The field of DNA nanotechnology has emerged to a high level of maturity and currently constitutes one of the most dynamic, creative, and exciting modern research areas. The transformation from structural DNA nanotechnology to functional DNA architectures is already taking place with tremendous pace. Particularly the advent of DNA origami technology has propelled DNA nanotechnology forward. DNA origami provided a versatile method for precisely aligning structural and functional DNA modules in two and three dimensions, thereby serving as a means for constructing scaffolds and chassis required for the precise orchestration of multiple functional DNA architectures. Key modules of these will contain interlocked nanomechanical components made of DNA. The mechanical interlocking allows for performing highly specific and controlled motion, by reducing the dimensionality of diffusion-controlled processes without restrictions in motional flexibility. Examples for nanoscale interlocked DNA architectures illustrate how elementary functional units of future nanomachines can be designed and realized, and show what role interlocked DNA architectures may play in this endeavor. Functional supramolecular systems, in general, and nanomachinery, in particular, self-organize into architectures that reflect different levels of complexity with respect to their function, their arrangement in the second and third dimension, their suitability for different purposes, and their functional interplay. Toward this goal, DNA nanotechnology and especially the DNA origami technology provide opportunities for nanomechanics, nanorobotics, and nanomachines. In this Account, we address approaches that apply to the construction of interlocked DNA nanostructures, drawing largely form our own contributions to interlocked architectures based on double-stranded (ds) circular geometries, and describe progress, opportunities, and challenges in rotaxanes and pseudorotaxanes made of dsDNA. Operating nanomechanical devices in a reliable and repetitive fashion requires methods for switching movable parts in DNA nanostructures from one state to another. An important issue is the orthogonality of switches that allow for operating different parts in parallel under spatiotemporal control. A variety of switching methods have been applied to switch individual components in interlocked DNA nanostructures like rotaxanes and catenanes. They are based on toehold, light, pseudocomplementary peptide nucleic acids (pcPNAs), and others. The key issues discussed here illustrate our perspective on the future prospects of interlocked DNA-based devices and the challenges that lay ahead.

Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism.

Three shape-persistent naphthylene-phenylene-acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior.

Mono- and multilayers of molecular spoked carbazole wheels on graphite.

Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system) and its synthetic precursor are investigated by scanning tunneling microscopy (STM) at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes - depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer.

Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles.

Conjugated polymers offer potential for many diverse applications, but we still lack a fundamental microscopic understanding of their electronic structure. Elementary photoexcitations (excitons) span only a few nanometres of a molecule, which itself can extend over microns, and how their behaviour is affected by molecular dimensions is not immediately obvious. For example, where is the exciton formed within a conjugated segment and is it always situated on the same repeat units? Here, we introduce structurally rigid molecular spoked wheels, 6 nm in diameter, as a model of extended π conjugation. Single-molecule fluorescence reveals random exciton localization, which leads to temporally varying emission polarization. Initially, this random localization arises after every photon absorption event because of temperature-independent spontaneous symmetry breaking. These fast fluctuations are slowed to millisecond timescales after prolonged illumination. Intramolecular heterogeneity is revealed in cryogenic spectroscopy by jumps in transition energy, but emission polarization can also switch without a spectral jump occurring, which implies long-range homogeneity in the local dielectric environment.