Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling.

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p-Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA-15 support, using a precise impregnation method. The unique design of the p-Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high-value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ gRu -1 ⋅ h-1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.

Cove-Edged Graphene Nanoribbons with Incorporation of Periodic Zigzag-Edge Segments.

Structurally precision graphene nanoribbons (GNRs) are promising candidates for next-generation nanoelectronics due to their intriguing and tunable electronic structures. GNRs with hybrid edge structures often confer them unique geometries associated with exotic physicochemical properties. Herein, a novel type of cove-edged GNRs with periodic short zigzag-edge segments is demonstrated. The bandgap of this GNR family can be tuned using an interplay between the length of the zigzag segments and the distance of two adjacent cove units along the opposite edges, which can be converted from semiconducting to nearly metallic. A family member with periodic cove-zigzag edges based on N = 6 zigzag-edged GNR, namely 6-CZGNR-(2,1), is successfully synthesized in solution through the Scholl reaction of a unique snakelike polymer precursor (10) that is achieved by the Yamamoto coupling of a structurally flexible S-shaped phenanthrene-based monomer (1). The efficiency of cyclodehydrogenation of polymer 10 toward 6-CZGNR-(2,1) is validated by FT-IR, Raman, and UV-vis spectroscopies, as well as by the study of two representative model compounds (2 and 3). Remarkably, the resultant 6-CZGNR-(2,1) exhibits an extended and broad absorption in the near-infrared region with a record narrow optical bandgap of 0.99 eV among the reported solution-synthesized GNRs. Moreover, 6-CZGNR-(2,1) exhibits a high macroscopic carrier mobility of ∼20 cm2 V-1 s-1 determined by terahertz spectroscopy, primarily due to the intrinsically small effective mass (m*e = m*h = 0.17 m0), rendering this GNR a promising candidate for nanoelectronics.

Detection and Stabilization of a Previously Unknown Two-Dimensional (Pseudo)polymorph using Lateral Nanoconfinement.

We report on the detection and stabilization of a previously unknown two-dimensional (2D) pseudopolymorph of an alkoxy isophthalic acid using lateral nanoconfinement. The self-assembled molecular networks formed by the isophthalic acid derivative were studied at the interface between covalently modified graphite and an organic solvent. When self-assembled on graphite with moderate surface coverage of covalently bound aryl groups, a previously unknown metastable pseudopolymorph was detected. This pseudopolymorph, which was presumably "trapped" in between the surface bound aryl groups, underwent a time-dependent phase transition to the stable polymorph typically observed on pristine graphite. The stabilization of the pseudopolymorph was then achieved by using an alternative nanoconfinement strategy, where the domains of the pseudopolymorph could be formed and stabilized by restricting the self-assembly in nanometer-sized shallow compartments produced by STM-based nanolithography carried out on a graphite surface with a high density of covalently bound aryl groups. These experimental results are supported by molecular mechanics and molecular dynamics simulations, which not only provide important insight into the relative stabilities of the different structures, but also shed light onto the mechanism of the formation and stabilization of the pseudopolymorph under nanoscopic lateral confinement.

Transfer of chiral information from a chiral solvent to a two-dimensional network.

Chiral induction in self-assembled monolayers has garnered considerable attention in the recent past, not only due to its importance in chiral resolution and enantioselective heterogeneous catalysis but also because of its relevance to the origin of homochirality in life. Here, we demonstrate the emergence of homochirality in a supramolecular low-density network formed by achiral molecules at the interface of a chiral solvent and an atomically-flat achiral substrate. We focus on the impact of structure and functionality of the adsorbate and the chiral solvent on the chiral induction efficiency in self-assembled physisorbed monolayers, as revealed by scanning tunneling microscopy. Different induction mechanisms are proposed and evaluated, with the assistance of advanced molecular modeling simulations.

Synthesis, Properties, and Two-Dimensional Adsorption Characteristics of [6]Hexahelicene-7-carboxylic acid.

A convergent synthesis of racemic [6]hexahelicene-7-carboxylic acid by cross-coupling of a bicyclic and a tricyclic component is described. A metal-catalyzed ring-closure is also a fundamental component of the synthetic approach. Scanning tunneling microscopy (STM) measurements of the racemate self-assembled on Au(111) at liquid-solid interface revealed the formation of ordered racemic 2D crystals.

Multicomponent self-assembly with a shape-persistent N-heterotriangulene macrocycle on Au(111).

Multicomponent network formation by using a shape-persistent macrocycle (MC6) at the interface between an organic liquid and Au(111) surface is demonstrated. MC6 serves as a versatile building block that can be coadsorbed with a variety of organic molecules based on different types of noncovalent interactions at the liquid-solid interface. Scanning tunneling microscopy (STM) reveals the formation of crystalline bicomponent networks upon codeposition of MC6 with aromatic molecules, such as fullerene (C60) and coronene. Tetracyanoquinodimethane, on the other hand, was found to induce disorder into the MC6 networks by adsorbing on the rim of the macrocycle. Immobilization of MC6 itself was studied in two different noncovalently assembled host networks. MC6 assumed a rather passive role as a guest and simply occupied the host cavities in one network, whereas it induced a structural transition in the other. Finally, the central cavity of MC6 was used to capture C60 in a complex three-component system. Precise immobilization of organic molecules at discrete locations within multicomponent networks, as demonstrated here, constitutes an important step towards bottom-up fabrication of functional surface-based nanostructures.

On the stability of surface-confined nanoporous molecular networks.

Self-assembly of molecular building blocks into two-dimensional nanoporous networks has been a topic of broad interest for many years. However, various factors govern the specific outcome of the self-assembly process, and understanding and controlling these are key to successful creation. In this work, the self-assembly of two alkylated dehydrobenzo[12]annulene building blocks was compared at the liquid-solid interface. It turned out that only a small chemical modification within the building blocks resulted in enhanced domain sizes and stability of the porous packing relative to the dense linear packing. Applying a thermodynamic model for phase transition revealed some key aspects for network formation.

Switching of single-molecule magnetic properties of TbIII -porphyrin double-decker complexes and observation of their supramolecular structures on a carbon surface.

Double-decker complexes based on single-molecule magnets (SMMs) are a class of highly promising molecules for applications in molecular spintronics, wherein control of both the ligand oxidative states and the 2D supramolecular structure on carbon materials is of great importance. This study focuses on the synthesis and study of 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP)-Tb(III) double-decker complexes with different electronic structures comprising protonated, anionic, and radical forms. Magnetic susceptibility measurements revealed that only the anionic and radical forms of the OEP-Tb(III) double-decker complexes exhibited SMM properties. The barrier heights for magnetic moment reversal were estimated to be 207 and 215 cm(-1) for the anionic and radical forms, respectively. Scanning tunneling microscopy (STM) investigations revealed that these OEP-Tb(III) complexes form well-ordered monolayers upon simple dropcasting from dilute dichloromethane solutions. All three complexes form an isomorphic pseudo-hexagonal 2D pattern, regardless of the differences in the electronic structures of their porphyrin-Tb cores. This finding is of interest for SMM technology as ultrathin films of these materials undergoing chemical transformations will not require any detrimental reorganization. Finally, we demonstrate self-assembly of the protonated 5,15-bisdodecylporphyrin (BDP)-Tb(III) double-decker complex as an example of successful supramolecular design to achieve controlled alignment of SMM-active sites.

Squeezing, then stacking: from breathing pores to three-dimensional ionic self-assembly under electrochemical control.

We demonstrate the spontaneous and reversible transition between the two- and three-dimensional self-assembly of a supramolecular system at the solid-liquid interface under electrochemical conditions, using in situ scanning tunneling microscopy. By tuning the interfacial potential, we can selectively organize our target molecules in an open porous pattern, fill these pores to form an auto-host-guest structure, or stack the building blocks in a stratified bilayer. Using a simple electrostatic model, we rationalize which charge density is required to enable bilayer formation, and conversely, which molecular size/charge ratio is necessary in the design of new building blocks. Our results may lead to a new class of electrochemically controlled dynamic host-guest systems, artificial receptors, and smart materials.

Micro-patterning of C-C covalently-bound grafts by mechanochemical imprint lithography.

A simple, inexpensive and versatile patterned removal of C-C grafts has been realized for scalable multicomponent micropatterned functionalization.

Spontaneous and scanning-assisted desorption-adsorption dynamics in porous supramolecular networks at the solution-solid interface.

Self-assembled molecular networks (SAMNs) are formed by the spontaneous assembly of molecules on surfaces. On conductive atomically flat surfaces, and also at the liquid-solid interface, scanning tunneling microscopy (STM) can follow their growth dynamics. Desorption and adsorption dynamics are difficult to probe through the liquid-solid interface. Porous molecular networks are of particular interest because they may act as platforms for sensing and host-guest chemistry. Very little is known though about their stability, particularly in a liquid environment. To this end, we have investigated the desorption/adsorption dynamics of supramolecular porous monolayers of alkoxylated dehydrobenzo[12]annulene (DBA) derivatives at the interface between highly oriented pyrolytic graphite, the substrate, and 1-phenyloctane, the liquid. To trace the dynamics, structurally analogous chiral DBA derivatives were used as marker molecules, which co-assemble with the achiral ones forming the supramolecular network. This approach reveals the time scales of the adsorption/desorption dynamics, the significance of temperature, and the important role of the STM tip in inducing dynamics.

Mastering fundamentals of supramolecular design with carboxylic acids. Common lessons from X-ray crystallography and scanning tunneling microscopy.

Hydrogen bonding is one of the most important non-covalent interactions in both biological (DNA, peptides, saccharides etc.) and artificial systems (various soft materials, host-guest architectures, molecular networks, etc.). Carboxylic acids are some of the most simple yet powerful hydrogen-bonding building blocks, that possess a particularly rich supramolecular chemistry. This tutorial review focuses on the structural diversity of supramolecular architectures accessible via hydrogen bonding of carboxylic acids, as observed both in single crystals using X-ray analysis and in monolayers on surfaces using scanning probe techniques. It provides a concise overview of the key concepts and principles of modern supramolecular design and is given in the form of case studies of finely selected literature examples, covering formation of macrocycles, chains, ladders, rotaxanes, catenanes, various 2D and 3D nets, host-guest systems and some applications thereof.

Defect-engineered surfaces to investigate the formation of self-assembled molecular networks.

Herein we report the impact of covalent modification (grafting), inducing lateral nanoconfinement conditions, on the self-assembly of a quinonoid zwitterion derivative into self-assembled molecular networks at the liquid/solid interface. At low concentrations where the compound does not show self-assembly behaviour on bare highly oriented pyrolytic graphite (HOPG), close-packed self-assembled structures are visualized by scanning tunneling microscopy on covalently modified HOPG. The size of the self-assembled domains decreases with increasing the density of grafted molecules, i.e. the molecules covalently bound to the surface. The dynamics of domains are captured with molecular resolution, revealing not only time-dependent growth and shrinkage processes but also the orientation conversion of assembled domains. Grafted pins play a key role in initiating the formation of on-surface molecular self-assembly and their stabilization, providing an elegant route to study various aspects of nucleation and growth processes of self-assembled molecular networks.

Supramolecular ordering in oligothiophene-fullerene monolayers.

Scanning tunneling microscopy (STM) of monolayers comprising oligothiophene and fullerene molecular semiconductors reveals details of their molecular-scale phase separation and ordering with potential implications for the design of organic electronic devices, in particular future bulk heterojunction solar cells. Prochiral terthienobenzenetricarboxylic acid (TTBTA) self-assembles at the solution/graphite interface into either a porous chicken wire network linked by dimeric hydrogen bonding associations of COOH groups (R(2)(2) (8)) or a close-packed network linked in a novel hexameric hydrogen bonding motif (R(6)(6) (24)). Analysis of high-resolution STM images shows that the chicken wire phase is racemically mixed, whereas the close-packed phase is enantiomerically pure. The cavities of the chicken wire structure can efficiently host C60 molecules, which form ordered domains with either one, two, or three fullerenes per cavity. The observed monodisperse filling and long-range co-alignment of fullerenes is described in terms of a combination of an electrostatic effect and the commensurability between the graphite and molecular network, which leads to differentiation of otherwise identical adsorption sites in the pores.

Supramolecular assembly of heterocirculenes in 2D and 3D.

The results of a high-resolution ambient STM study of 'sulflower' (octathio[8]circulene) and 'selenosulflower' (sym-tetraselena-tetrathio[8]circulene) molecules, immobilized in a hydrogen-bonded matrix of trimesic acid (TMA) at the solid-liquid interface, are compared with the STM and X-ray structure of separate host and guest 2D and 3D crystals, respectively.

Phase selectivity triggered by nanoconfinement: the impact of corral dimensions.

By using a novel protocol to spatially confine molecules in well-defined small 2D areas, the so-called nanocorrals, we show using scanning tunneling microscopy (STM) how this kind of confinement affects self-assembled molecular network (SAMN) formation at a liquid-solid interface. The 2D lateral confinement, imposed by the size of the nanocorrals, has a clear impact on the phase selectivity of a molecule that can form both low-density and high-density SAMNs, the high-density phase being promoted by the confinement.

Halogenated building blocks for 2D crystal engineering on solid surfaces: lessons from hydrogen bonding.

Halogen bonding has emerged as a promising tool in two-dimensional (2D) crystal engineering. Since halogen bonds are similar to hydrogen bonds in a number of aspects, the existing knowledge of hydrogen bonded systems can be applied to halogenated systems. Here we evaluate the applicability of a retrosynthetic approach based on topological similarity between hydrogen and halogen bonds to obtain predictable halogen bonded networks. The self-assembly of 1,3-dibromo-5-alkoxybenzene derivatives was studied in analogy with well-explored alkoxy isophthalic acids using a combination of experimental and theoretical tools. Scanning tunneling microscopy (STM) characterization of the networks formed at the liquid-graphite interface revealed that while the retrosynthetic approach works at the level of small clusters of molecules within the 2D network, the overall structure of the network deviates from the anticipated structure. The monolayers consist of fractured rows of halogen-bonded modules instead of the expected continuous lamellar structure. Each module consists of a discrete number of halogen-bonded molecules. The interactions responsible for the stabilization of halogen bonded dimers are delineated through detailed density functional theory (DFT) calculations coupled with natural bonding orbitals (NBO) and perturbation analysis. A modified force field that includes an extra charged site to imitate the σ hole on the halogen atom was developed and applied to extract total potential energies of the anticipated and observed networks. Plausible reasons for the deviation from the anticipated structure are discussed. Finally, a modified molecular design that allows successful application of the hydrogen bond-halogen bond analogy was tested experimentally.

Graphite and Graphene Fairy Circles: A Bottom-Up Approach for the Formation of Nanocorrals.

A convenient covalent functionalization approach and nanopatterning method of graphite and graphene is developed. In contrast to expectations, electrochemically activated dediazotization of a mixture of two aryl diazonium compounds in aqueous media leads to a spatially inhomogeneous functionalization of graphitic surfaces, creating covalently modified surfaces with quasi-uniform spaced islands of pristine graphite or graphene, coined nanocorrals. Cyclic voltammetry and chronoamperometry approaches are compared. The average diameter (45-130 nm) and surface density (20-125 corrals/µm2) of these nanocorrals are tunable. These chemically modified nanostructured graphitic (CMNG) surfaces are characterized by atomic force microscopy, scanning tunneling microscopy, Raman spectroscopy and microscopy, and X-ray photoelectron spectroscopy. Mechanisms leading to the formation of these CMNG surfaces are discussed. The potential of these surfaces to investigate supramolecular self-assembly and on-surface reactions under nanoconfinement conditions is demonstrated.

Alkyl chain length effects on double-deck assembly at a liquid/solid interface.

Controlled double-deck packing is an appealing means to expand upon conventional 2D self-assembly which is critical in crystal engineering, yet it is rare and poorly understood. Herein, we report the first systematic study of double-deck assembly in a series of alkylated aminoquinone derivatives at the liquid-solid interface. The competition between the fraction of alkyl chains adsorbed on the surface and the optimal conformation of the alkyl chains near the head group leads to a stepwise structural transformation ranging from complete double-deck packing to complete monolayer packing. Alkyl chains on the bottom or top layer of the double-deck assemblies were selectively visualized by carefully tuning the scanning tunneling microscopy settings. A method to easily identify mirror image domains was discovered based on the coincidence of domain boundaries with a graphite main axis. The effect of molecular symmetry and metal complexation on the formation of the double-deck assembly was also explored. Based on 2D crystal engineering principles, this bottom-up double-deck assembly can potentially provide an essential toehold for constructing precise 3D hierarchical structures.

Computational insight into the origin of unexpected contrast in chiral markers as revealed by STM.

Internal substituents can serve the double purpose of generating stereogenic centers and (potentially) being identifiable with Scanning Tunneling Microscopy (STM) in 2D self-assembled molecular layers. We investigate computationally the origin of stark contrast variations in STM images of chirally substituted self-assembled organic films. STM images of alkyl derivatives with secondary -CH3 and -OH groups have been simulated. Density functional theory calculations reveal bias-dependent contrast reversals in the substituent regions: a lack of local density of states in the relevant energy regime results in 'dark spots' in the simulated STM images, which turn bright upon increasing the bias voltage.