Symmetry of Pyridine Derivatives Controlled Two-Dimensional Nanostructural Diversity by Co-Assembly with Aromatic Carboxylic Acids.

The self-assembly behaviors of aromatic carboxylic acids are commonly investigated at the liquid/solid interfaces because of their rigid skeletons and both hydrogen-bond donors and receptors. However, self-assemblies of aromatic carboxylic acids with low symmetry and interactions between carboxylic acid and pyridine derivatives are worth exploring. In this work, the self-assembled structural transitions of a kind of low-symmetric aromatic carboxylic acid (H4QDA) are regulated by the coadsorption of two pyridine derivatives (DPE and T4PT) with different symmetry, which are investigated by scanning tunneling microscopy under ambient conditions. For the H4QDA/DPE system, the grid structure appears. For the H4QDA/T4PT system, the coassembled morphologies display an obvious concentration dependence. With the increase of solution concentration of T4PT, three coassembled patterns (network structure, chiral linear structure, and brick-like structure) are observed. Corresponding structural models suggest that the O-H···N hydrogen bonds have great contributions to stabilizing these coassembled structures. Our studies will help to explore the complexity, diversity, and functionality of multiple component systems and are conducive to further understanding the underlying mechanisms in the assembly process.

Surface-supported metal-organic frameworks with geometric topological diversity via scanning tunneling microscopy.

Surface-supported metal-organic frameworks (SMOFs) are long-range ordered periodic 2D lattice layers formed by inorganic metal nodes and organic ligands via coordination bonds on substrate surfaces. The atomic resolution STM lays a solid foundation for the conception and construction of SMOFs with large area, stable structure, and special function. In this review, the cutting-edge research of SMOFs from design strategy, preparation process, and how to accurately achieve structural and functional diversity are reviewed. Furthermore, we focus on the design and construction of novel and fascinating periodic and fractal structures, in which some typical honeycomb structures, Kagome lattice, hexagonal geometry, and Sierpinski triangles are summarized, and the related prospects for designing functional nanoscale systems and architectures are prospected. Finally, the challenges faced in the design and synthesis of SMOFs are denoted, and the application prospect and development trend of SMOFs are forecasted based on the current research status.

Terminal Group Effect on Two-Dimensional Self-Assembly of Fluorenone-Based Liquid Crystals at the Solid/Liquid Interface.

Self-assemblies of two fluorenone-based derivatives (FE and FEC) consisting of a central 2,7-diphenyl-9-fluorenone polar moiety but differing in the flexible terminal groups were investigated by scanning tunneling microscopy (STM) at the 1-octanoic acid/HOPG interface under different concentrations and density functional theory calculation (DFT). STM results reveal a concentration-dependent polymorphic self-assembly behavior for FE, but without the presence of co-adsorbed solvents. As the concentration decreases, the dimer, bracket-like, and ribbon-like self-assembled structures were observed. On the contrary, FEC molecules assemble into only a type of oval-shaped morphology by the intermolecular N···H-O hydrogen bonds with the solvent molecules. Combined with DFT calculations, it can be deduced that the intermolecular van der Waals forces, dipole-dipole interactions, and hydrogen bonding are the main driving forces to stabilize the molecular packing of fluorenone-based polycatenars with strong polarity. Our work is of significance at the molecular level to further clarify the intermolecular interactions and conformational effects on the formation of molecular packing structures with liquid crystal property.

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative.

Halogen bonding (XB) is of great importance in fabricating a two-dimensional (2D) self-assembly for its adaptive directionality. However, the XBs involving fluorine (F) have barely been studied due to the absence of an σ-hole on F. Here, 2D self-assemblies of a F-substituted 4,7-bis(5-bromo-4-dodecylthiophen-2-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole (BTZ-BrF) molecule on graphite were investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM experiments revealed that the 2D patterns of BTZ-BrF had a clear solvent and concentration dependence, showing a frame-like pattern in aliphatic acid and aliphatic hydrocarbon solvents at high concentrations. At lower concentrations, a bamboo-like and a wave-like pattern were observed in aliphatic acid, whereas small frame-like and large ladder-like domains at high solution concentrations in aliphatic hydrocarbon were observed. As the concentration further decreased, two linear patterns were observed. DFT calculations suggested that the hetero-XBs of F···Br, F···S, Br···S, and Br···N, the homo-XBs of type-II Br···Br, and the S···S interactions synergistically directed and stabilized the polymorphic 2D architectures. This understanding of intermolecular XBs during the molecular assembly at the molecular level may shed light on the ongoing efforts of regulating nanostructures of multifunctional organics.

Different Stepwise Growth Mechanism of AIE-Active Tetraphenylethylene-Functionalized Metal-Organic Frameworks on Au(111) and Cu(111) Surfaces.

Fabricating tetraphenylethylene (TPE)-functionalized metal-organic frameworks (MOFs) with aggregation- induced emission on surfaces and understanding the growth mechanism have not yet been pursued. Herein, MOFs constructed via the Ullmann-type reaction of a C2-symmetry TPE derivative (p-BrTBE) on Au(111) and Cu(111) surfaces were thoroughly investigated using scanning tunneling microscopy. On a Au(111) surface, p-BrTBE molecules formed the self-assembled pattern at 298 K. Stepwise annealing led to a progressive evolution process, in which the stepwise debromination reaction led to organometallic intermediates, and surface-stabilized radicals and metal-organic networks were formed. By contrast, the relatively ordered MOFs were obtained by replacing the underlying substrate with the more catalytically active Cu(111) at 298 K. Density functional theory calculations demonstrated that the formation of different networks on Au(111) and Cu(111) was determined by the different conformations of the TBE unit on the different substrates due to the different adsorption energy.

Fabrication of robust superhydrophobic magnetic multifunctional coatings and liquid marbles.

To obtain durable and multi-function superhydrophobic surfaces, we reported a facial method to prepare a multifunctional suspension (γ-Fe2O3@SiO2@PDMS suspension) named as FSP suspension, in which γ-Fe2O3 was coated by the silica shell and PDMS was used as the outer layer. Superhydrophobic magnetic polyurethane (SMPU) sponge was prepared by immersing the polyurethane (PU) sponge into the FSP suspension, exhibiting the superior ability to absorb oil. In addition, it could also move directionally by the attraction of magnets and absorb the oil along the fixed path. The heated superhydrophobic magnetic stainless steel (H-SMSS) mesh was acquired by spraying FSP suspension onto the stainless steel mesh and then heating at 400 °C, which demonstrated superior superhydrophobicity and resistance to abrasion and chemical corrosion. Besides, the H-SMSS mesh displayed excellent flux and efficiency to separate the oil/water mixture. Rolling droplets on FSP particles, the superhydrophobic magnetic liquid marbles (SMLMs) were fabricated, in which liquids with different volumes were encapsulated and transported directionally. Further, it was convenient to inject liquid into the SMLM and withdraw liquid from it. Thus, the prepared FSP suspension has promising applications in constructing large-area, robust, and multifunctional surfaces and microreactors.

Chain-Length- and Concentration-Dependent Isomerization of Bithiophenyl-Based Diaminotriazine Derivatives in Two-Dimensional Polymorphic Self-Assembly§.

Bithiophenyl-based diaminotriazine derivatives (2TDT-n, n = 10, 12, 16, and 18) with different chain lengths display colhex/p6mm mesophases. Their supramolecular self-assembled mechanism is investigated using scanning tunneling microscopy (STM) at the 1-octanoic acid/graphite interface at various concentrations. The chain length effect on the two-dimensional adlayers is observed in this system, and 2TDT-n molecules show a structural phase transition from the four-leaf arrangement to the two-row linear nanostructure accompanied by the emergence of molecular isomerization with the increase of the side-chain length. The self-assembled structure of 2TDT-10 is composed of a four-leaf pattern with uniform s-cis conformers. In 2TDT-12, three kinds of nanostructures (bamboo-like, two-row linear pattern-I, and flower-like) are observed. These nanostructures are randomly constituted by cis and trans conformers, and the ratios of the s-cis conformer in three kinds of patterns are 55.7, 42.3, and 62.5%, respectively. Furthermore, when n = 16 and 18, the ratio of the s-cis conformer further decreases to 19.0 and 4.3%, respectively. Those molecules mainly form linear nanostructures consisting of s-trans conformers. Therefore, it is reasonable to conclude that the side-chain length has a great effect on the self-assembled patterns and the molecular conformation of bithiophenyl-based diaminotriazine derivatives. Density functional theory calculations are applied to optimize molecular conformers and assess their single-point energies, showing that the s-cis conformation has higher energy than the s-trans conformer. We speculate that the ratio of two conformers in nanostructures might be similar to that of the liquid crystalline phase.

Coronene and Phthalocyanine Trapping Efficiency of a Two-Dimensional Kagomé Host-Nanoarchitecture.

The trapping of coronene and zinc phthalocyanine (ZnPc) molecules at low concentration by a two-dimensional self-assembled nanoarchitecture of a push-pull dye is investigated using scanning tunneling microscopy (STM) at the liquid-solid interface. The push-pull molecules adopt an L-shaped conformation and self-assemble on a graphite surface into a hydrogen-bonded Kagomé network with porous hexagonal cavities. This porous host-structure is used to trap coronene and ZnPc guest molecules. STM images reveal that only 11% of the Kagomé network cavities are filled with coronene molecules. In addition, these guest molecules are not locked in the host-network and are desorbing from the surface. In contrast, STM results reveal that the occupancy of the Kagomé cavities by ZnPc evolves linearly with time until 95% are occupied and that the host structure cavities are all occupied after few hours.

Stepwise on-surface synthesis of thiophene-based polymeric ribbons by coupling reactions and the carbon-fluorine bond cleavage.

The rational synthesis of thiophene-based cross-coupled polymers on surfaces has been attracting more attention recently. Here, we report the stepwise activation of 5,5'-(2,3-difluoro-1,4-phenylene)bis(2-bromothiophene) as a precursor to synthesize thiophene-based polymeric ribbons on the Au(111) surface. Scanning tunneling microscopy studies showed that the precursor adopted different conformations in the self-assembled structure, organometallic species, and covalent polymers. On annealing the sample at a relatively low temperature (150 °C), the conversion of the organometallic structure into a covalent product with straight lines was observed, in which the Br adatoms arranged between the neighboring chains. On further annealing the sample at 270 °C, the detached Br adatoms played a key role in promoting the C-H bond activation. The cross-linked polymer was achieved by a combination of Ullmann and dehydrogenative coupling. When the annealing temperature was up to 390 °C, the C-F bond activation was triggered, which led to the formation of polymeric ribbons resulting from the cyclodehydrogenation of the fluorinated polymer. This study further supplements the reaction mechanism of thiophene-based dehalogenative, dehydrogenative and defluorinative coupling, and provides us a rational way for synthesizing cross-linked functional materials.

Template-assisted 2D self-assembled chiral Kagomé network for selective adsorption of coronene.

Solvent molecules (n-tridecane and n-tetradecane) act as templates by coadsorption to direct the assembly of asymmetric 2-bisthienyl-4,6-diamino-1,3,5-triazine into chiral Kagomé networks. Furthermore, guest molecules (coronene) fill in the hexagonal voids by replacing the solvent molecules due to the selective and competitive adsorption behavior.

Conformation modification of terthiophene during the on-surface synthesis of pure polythiophene.

On-surface coupling under ultra-high vacuum is employed as a versatile approach to synthesize pure polythiophene from a 5,5''-dibromo-2,2':5',2''-terthiophene (DBTT) precursor and the corresponding temperature-dependent stepwise reaction mechanism is systematically studied by scanning tunneling microscopy (STM). After thermal deposition of the precursor onto a Au(111) surface that is kept at room temperature, a triangle-like pattern and a linear self-assembled pattern are formed with different molecular coverages through BrBrS halogen bonds and BrBr type-I contact bonds, respectively. In the self-assembled nanostructures, the thiophene units adopt trans-conformation. Mild annealing promotes the structural transition of both nanostructures into ordered zigzag organometallic linear chains with all-cis configured thiophene units connected through coordination bonds to the Au adatoms. Such conformational variety is easily recognized by STM, particularly in the case of DBTT-CH3 with the extra -CH3 signals. The covalently coupled products from the DBTT precursor are obtained by further annealing the organometallic intermediate at higher temperatures, which leads to the removal of Au atoms and the formation of ordered polymer chains and disordered polythiophene networks. Further characterization suggests that the reaction mechanism is associated with Ullmann-type coupling to form the ordered chains as well as Ullmann-type and dehydrogenative C-C coupling to fabricate cross-linked polymer networks. Compared with the on-surface synthesis process of DBTT on the Cu(111) surface, it can be confirmed that the Au adatoms are vital to synthesize polythiophene. These findings provide important insight into the reaction mechanism of on-surface synthesized pure polythiophene and on-surface coupling can potentially be applied to synthesize other functional conjugated polymers.

The Brπ halogen bond assisted self-assembly of an asymmetric molecule regulated by concentration.

The two-dimensional (2D) self-assembly behavior of an asymmetric thienophenanthrene derivative (M1) has been theoretically predicted and further probed via STM. The barely exploited Brπ halogen bonds play an assisting role in the structural formation, and a strong cooperative effect from the C-HBr bonds is shown. Such π-type halogen bond assisted self-assembly reveals self-adaption properties, which is of great interest for flexible light-emitting devices and self-healing materials.

Ordering self-assembly structures via intermolecular BrS interactions.

Recent research studies have shown that the halogenated benzo[1,2-b:4,5-b']dithiophene (DTBDT) unit as a polymer donor exhibits high charge carrier mobility due to the well-ordered molecular packing and high crystallinity, which is meaningful for achieving highly efficient organic solar cells (OSCs). However, it is difficult to acquire the accurate packing information of polymer materials. Herein, we investigated the self-assembled behaviors of two DTBDT derivatives, 4,8-bis(4-octadecylthiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (H-DTBDT) and 4,8-bis(5-bromo-4-octadecylthiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (Br-DTBDT), to elucidate the effect of introducing a bromine atom on molecular packing structures by STM at the 1-phenyloctane/HOPG interface. It is observed that the H-DTBDT molecules exhibit a random arrangement along each lamella, while the Br-DTBDT molecules self-assemble into a highly ordered lamellar structure. Density functional theory (DFT) analysis combined with the topological properties of the electron density at the bond critical points revealed that the existence of weak intermolecular interactions of BrS facilitates the regular packing motif of Br-DTBDT molecules. The results helped us to understand that the BrS bond generally acted as the auxiliary force and can play the primary role in the construction of supramolecular nanostructures.

Same building block, but diverse surface-confined self-assemblies: solvent and concentration effects-induced structural diversity towards chirality and achirality.

Fabricating complex nano-networks on solid substrates is a research area that has attracted much attention in the field of molecular self-assembly. By designing a fluorenone derivative of 2-heptyloxy-7-pentadecyloxy-9-fluorenone (HPF), we obtained a surface-confined system that presented diverse nanostructures. The assembled networks for HPF were highly dependent on the solvent and concentration. At the liquid/solid interface, chiral tetramer-S, hexamer-S, and tetramer-linear structures as well as achiral irregular-linear and random structures were recorded. On the dry surface, we observed chiral octamer-S and achiral alternate configurations. During the self-assembly process, the short and long alkyl chains of HPF showed selective identification, which contributed to the formation of S-like or anti-S-like tetramers, hexamers and octamers, resulting in chiral structures. The nanopatterns were stabilized under the driving forces of dipolar interactions, hydrogen bonds and van der Waals interactions. Moreover, we performed forcefield calculations in order to further understand the underlying mechanisms from the viewpoints of their force strengths and binding energies. In general, the present work provides a significant impetus to induce polymorphous structures, and we believe that it will promote the study of chirality and achirality in the field of molecular self-assembly.

Chiral polymorphism in the self-assemblies of achiral molecules induced by multiple hydrogen bonds.

Owing to a wide range of applications within the areas such as chiral sensors, enantiomeric resolution, and asymmetric catalysis, understanding chiral adsorption phenomena at the interface is thereby of great importance. In particular, the role of multiple hydrogen bonds in inducing chiral diversiform morphologies has never been systematically investigated. Herein, by delicate control of the volume ratio of 1-octanoic acid and 1-octanol as the mixed solvent, a series of self-assembled nanostructures of 2-hydroxyl-7-pentadecyloxy-fluorenone (HPF) were sequentially fabricated, including the achiral densely-packed pattern, the chiral "6-2" pattern, the chiral alternate pattern, and the chiral double-rosette pattern. Eventually, those patterns would evolve into an achiral and thermodynamically favored zigzag pattern. Based on DFT calculations, we demonstrate that the stabilities of diversiform morphologies originate from different hydrogen bonding and molecular packing densities. In addition, quantum theory of atoms in molecule (QTAIM) analysis is further applied to interpret the nature of these hydrogen bonds.

Highly efficient separation of surfactant stabilized water-in-oil emulsion based on surface energy gradient and flame retardancy.

HYPOTHESIS: Surface energy gradient would generate an imbalance force to drive tiny water droplets in dry air from the hydrophilic bumps to superhydrophobic domains, which has found on the Stenocara beetle's back. EXPERIMENTS: Inspired by this phenomenon, we introduced a pristine superhydrophilic filter paper on the lower surface energy superhydrophobic filter paper. ZnSn(OH)6 particles and polydimethylsiloxane were mixed to prepare the superhydrophobic coating, and the coating was spray-coated on the poly(dialkyldimethylammonium chloride) covered filter paper to separate the span 80 stabilized water-in-isooctane emulsion. A pristine filter paper was added on the superhydrophobic filter paper to fabricate another membrane for separation. FINDINGS: The results revealed that with a pristine filter paper, the membrane performed higher efficiency and more recyclability, and it could separate the emulsions with higher surfactant concentrations. The stabilized water droplets passed the superamphiphilic surface, and hindered by the superhydrophobic surface, generating a surface energy gradient for better separation. In addition, the superhydrophobic membrane could be protected from fire to some degree due to the introduced ZnSn(OH)6 particles with excellent flame retardancy. This easy and efficient approach via simply bringing in pristine superhydrophilic membrane has great potential applications for water-in-oil emulsion separation or oil purification.

Cooperating dipole-dipole and van der Waals interactions driven 2D self-assembly of fluorenone derivatives: ester chain length effect.

Two-dimensional supramolecular assemblies of a series of 2,7-bis(10-n-alkoxycarbonyl-decyloxy)-9-fluorenone derivatives (BAF-Cn, n = 1, 3-6) consisting of polar fluorenone moieties and ester alkoxy chains were investigated by scanning tunneling microscopy on highly oriented pyrolytic graphite surfaces. The chain-length effect was observed in the self-assembly of BAF-Cn. Self-assembly of BAF-C1 was composed of a linear I pattern, where the side chains adopted a fully interdigitated arrangement. As the length of side chains increased, the coexistence of a linear I pattern and a cyclic pattern for the self-assembly of BAF-C3 was observed. Upon increasing the length of the alkoxy chain even further (n = 4-6), another linear II structure was observed in the BAF-Cn monolayer, in which the side chains in adjacent rows were arranged in a tail-to-tail configuration. It is reasonable to conclude that not only the van der Waals forces but also the dipole-dipole interactions from both the fluorenone cores and the ester alkoxy chains play critical roles in the self-assemblies of BAF-Cn. Our work provides detailed insights into the effect of intermolecular dipole-dipole and van der Waals interactions on the monolayer morphology of fluorenone derivatives.

Robust and thermal-healing superhydrophobic surfaces by spin-coating of polydimethylsiloxane.

HYPOTHESIS: Superhydrophobic surfaces easily lose their excellent water-repellency after damages, which limit their broad applications in practice. Thus, the fabrication of superhydrophobic surfaces with excellent durability and thermal healing should be taken into consideration. EXPERIMENTS: In this work, robust superhydrophobic surfaces with thermal healing were successfully fabricated by spin-coating method. To achieve superhydrophobicity, cost-less and fluoride-free polydimethylsiloxane (PDMS) was spin-coated on rough aluminum substrates. FINDINGS: After being spin-coated for one cycle, the superhydrophobic PDMS coated hierarchical aluminum (PDMS-H-Al) surfaces showed excellent tolerance to various chemical and mechanical damages in lab, and outdoor damages for 90days. When the PDMS-H-Al surfaces underwent severe damages such as oil contamination (peanut oil with high boiling point) or sandpaper abrasion (500g of force for 60cm), their superhydrophobicity would lose. Interestingly, through a heating process, cyclic oligomers generating from the partially decomposed PDMS acted as low-surface-energy substance on the damaged rough surfaces, leading to the recovery of superhydrophobicity. The relationship between the spin-coating cycles and surface wettability was also investigated. This paper provides a facile, fluoride-free and efficient method to fabricate superhydrophobic surfaces with thermal healing.

Two side chains, three supramolecules: exploration of fluorenone derivatives towards crystal engineering.

Structural diversity obtained through two-dimensional molecular self-assembly induced by the chain length effect has gained immense attention, not only because of its significance in crystal engineering but also for its potential application in nanoscience and nanotechnology. Three kinds of fluorenone derivative, named F-C7C7, F-C14C7, and F-C14C14, were synthesized and used for systematic exploration of their crystalline difference. At first, scanning electron microscopy and X-ray powder diffraction were performed to investigate their differences in morphology and three-dimensional crystal structure. Then scanning tunneling microscopy experiments were conducted to compare the self-assembled monolayers. Moreover, different solvents were used to repeatedly investigate the occurrence of structural diversity. F-C7C7 could not self-assemble into a stable monolayer on the graphite surface under ambient conditions due to its weak molecule-substrate interaction. F-C14C7 was observed to self-assemble into twist, plier-like, octamer-curve, and random structures in 1-octanoic acid, 1-phenyloctane, n-tetradecane, and dichloromethane, respectively. However, when the same solvents were used and at similar concentrations, the F-C14C14 molecules were arranged into interval, mixed, linear, and plier-like configurations. These self-assembled nanopatterns formed under the driving forces of dipole-dipole interactions, hydrogen bonds, and chain-chain, molecule-substrate, and molecule-solvent van der Waals interactions. Furthermore, from the viewpoint of thermal analysis, differential scanning calorimetry, as well as polarized optical microscopy, was performed to further elucidate the difference between these three compounds in the solid and liquid crystal states. The present system is believed to provide understanding of how the chain length effect induces different crystalline properties, and to open up the possibility of fabricating diverse self-assembled networks for crystal engineering.

One-Step Fabrication of Non-Fluorinated Transparent Super-Repellent Surfaces with Tunable Wettability Functioning in Both Air and Oil.

In this paper, we have developed a one-step thermal treatment of polydimethylsiloxane (PDMS) liquid to create transparent super-repellent surface (TSS) and super-repellent powder. They are super-repellent toward water and ethylene glycol. During the one-step thermal treatment, PDMS soot is generated and deposited onto a glass slide (GS) surface to fabricate the TSS without fluorosilane modification. The facilely obtained TSS presented superhydrophobicity and self-cleaning property when immersed into very low surface tension oils such as petroleum ether, hexadecane, peanut oil, and dodecane. Interestingly, by controlling heating time and temperature, wettability of the treated GS surface and the remained white powder can be regulated. The mechanism of tunable wettability was revealed and analyzed by investigating the variations of surface morphology and chemical composition. More importantly, TSS was able to repel highly corrosive aqua regia and saturated NaOH solutions. TSS maintained excellent superhydrophobicity even after chemical and mechanical damages. This simple thermal deposition method was also applicable for other thermally stable substrates to achieve super-repellency, which are believed to find very promising applications.