Study on 2D Molecular Networks of Flexible Pentacarboxylic Acid Ligands Induced by Ether Bonds in Response to Selective Guest Inclusion.

The flexibility of ligands allows for their bending, twisting, or rotation to adopt various conformations, leading to distinct symmetries during the self-assembled process. Flexible aromatic acid ligands modified by ether bonds are a promising type of self-assembled module when it comes to surfaces. Here, two pentacarboxylic acid ligands (H5L1 and H5L2) with minor skeleton differences have successfully self-assembled into disparate porous networks on the graphite surface and demonstrated excellent potential for the inclusion of guest molecules. The H5L1 molecule's network structure only accommodates coronene (COR) molecules. With fewer COR molecules, H5L1 molecules act as a host template to accommodate the COR molecules. When there are too many COR molecules, COR molecules will induce H5L1 molecules to transform into a new host-guest nanostructure. Additionally, H5L2 molecules showed the ability to capture C70 molecules and exhibited cavity selectivity. However, the assembled network of H5L2 was slightly deformed in attempts to trap the COR molecules. To understand these phenomena more deeply, various assembled mechanisms were analyzed in combination with building theoretical models and energy analysis. These results reveal the great potential of flexible aromatic acid ligands in two-dimensional self-assembly and host-guest systems for their application in related fields.

A Solution-Processable Porphyrin-Based Hydrogen-Bonded Organic Framework for Photoelectrochemical Sensing of Carbon Dioxide.

Detecting CO2 in complex gas mixtures is challenging due to the presence of competitive gases in the ambient atmosphere. Photoelectrochemical (PEC) techniques offer a solution, but material selection and specificity remain limiting. Here, we constructed a hydrogen-bonded organic framework material based on a porphyrin tecton decorated with diaminotriazine (DAT) moieties. The DAT moieties on the porphyrin molecules not only facilitate the formation of complementary hydrogen bonds between the tectons but also function as recognition sites in the resulting porous HOF materials for the selective adsorption of CO2 . In addition, the in-plane growth of FDU-HOF-2 into anisotropic molecular sheets with large areas of up to 23000 µm2 and controllable thickness between 0.298 and 2.407 µm were realized in yields of over 89 % by a simple solution-processing method. The FDU-HOF-2 can be directly grown and deposited onto different substrates including silica, carbon, and metal oxides by self-assembly in situ in formic acid. As a proof of concept, a screen-printing electrode deposited with FDU-HOF-2 was fabricate as a label-free photoelectrochemical (PEC) sensor for CO2 detection. Such a signal-off PEC sensor exhibits low detection limit for CO2 (2.3 ppm), reusability (at least 30 cycles), and long-term working stability (at least 30 days).

Sheet-like 2D Manganese(IV) Complex with High Photothermal Conversion Efficiency.

We report a stable, water-soluble, mononuclear manganese(IV) complex [MnIV(H2L)]·5H2O (Mn-HDCL) that acts as an efficient photothermal material. This system is based on a hexahydrazide clathrochelate ligand (L/HDCL) and is obtained via an efficient one-pot templated synthesis that avoids the need for harsh reaction conditions. Scanning tunneling microscopy images reveal that Mn-HDCL exists as a 2D sheet-like structure. In Mn-HDCL, the manganese(IV) ion is trapped within the cavity of the cage-like ligand. This effectively shields the Mn(IV) ion from the external environment while providing adequate water solubility. As a result of orbital transitions involving the coordinated manganese(IV) ion, as well as metal-to-ligand charge transfer effects, Mn-HDCL possesses a large extinction coefficient and displays a photothermal performance comparable to single-wall carbon nanotubes in the solid state. A high photothermal conversion efficiency (ca. 71%) was achieved in aqueous solution when subjected to near-infrared 730 nm laser photo-irradiation. Mn-HDCL is paramagnetic and provides a modest increase in the T1-weighted contrast of magnetic resonance images both in vitro and in vivo. Mn-HDCL was found to target tumors passively and allow tumor margins to be distinguished in vivo in a mouse model. In addition, it also exhibited an efficient laser-triggered photothermal therapy effect in vitro and in vivo. We thus propose that Mn-HDCL could have a role to play as a tumor-targeting photothermal sensitizer.

Co-assembly Behaviors of Flavonol Derivatives Induced by a Pyridine Derivative on HOPG via Hydrogen Bonding and Van der Waals Forces.

In this paper, two new flavonol derivatives, 2-(4-(dodecyloxy)phenyl)-3-hydroxyflavone (DHF) and 2-(3,5-bis(dodecyloxy)phenyl)-3-hydroxyflavone (BDHF), were synthesized to investigate the respective self-assembly behaviors at the liquid/solid interface by scanning tunneling microscopy. In addition, a linear pyridine derivative with acetylene groups called BisPy was added to regulate the assembly of DHF and BDHF, individually. However, only BDHF molecules successfully co-assembled into grid structures with BisPy molecules. Furthermore, the assembly and co-assembly behavior mechanism of flavonol derivatives and BisPy molecules were further studied by density functional theory calculations. This work will lay a foundation for investigating the self-assembly of flavonol derivatives and the co-assembly regulated by pyridine derivatives at the liquid-solid interface.

Self-Assembly of Triphenylamine Macrocycles and Co-assembly with Guest Molecules at the Liquid-Solid Interface Studied by STM: Influence of Different Side Chains on Host-Guest Interaction.

The side chains of macrocyclic molecules have a non-negligible effect on the two-dimensional (2D) supramolecular networks at the liquid-solid interface. In this study, we investigate the self-assembly behaviors of two conjugated triphenylamine macrocycles modified with different alkyl chains and construct the host-guest supramolecular nanopatterns on the highly oriented pyrolytic graphite with a scanning tunneling microscope. In combination with density functional theory calculations, how different side chains affect the host-guest interaction is discussed. This work provides insights into constructing a 2D host-guest dynamic co-assembly on the surface.

Regulation of the Assembled Structure of a Flexible Porphyrin Derivative Containing Tetra Isophthalic Acids by Coronene or Different Pyridines.

Based on previous research, a new coassembly formed by a porphyrin derivative (IPETPP), which contains a flexible substituent of m-phthalic acid, is observed with coronene (COR) molecules at a higher concentration. Besides, a fresh IPETPP self-assembly formed at a lower concentration and another new coassembly with COR molecules are obtained. Moreover, the addition of a series of bipyridines alters the diamond arrangement of IPETPP, which enhances the stability of the two-component structures. It is unprecedented that bipyridine derivatives break intermolecular hydrogen bonds containing m-phthalic acid substituents. All the coassemblies are investigated by scanning tunneling microscopy on a highly oriented pyrolytic graphite. Combined with density functional theory, the formation mechanism of the assembled structures is revealed. These results would contribute to understanding the interfacial crystal behaviors and probably provide an efficient pathway to regulate the binary structures.

Hydrogen-Bonded Organic Framework Ultrathin Nanosheets for Efficient Visible-Light Photocatalytic CO2 Reduction.

Post-modification of robust guanine-quadruplex-linked 2,2'-pyridine-containing HOF-25 with Ni(ClO4 )2 ⋅ 6 H2 O followed by exfoliation using sonication method affords hydrogen-bonded organic framework (HOF) nanosheets (NSs) of HOF-25-Ni in the yield of 56 %. TEM and AFM technologies disclose the ultrathin nature of HOF-25-Ni NSs with thickness of 4.4 nm. STM observation determines the presence of sql segments assembled from HOF-25-Ni building blocks at the heptanoic acid/highly oriented pyrolytic graphite interface, supporting the simulated 2D supramolecular framework. ICP-MS, XAS, and XPS data prove the successful immobilization of atomic nickel sites on the 20 % total 2,2'-pyridine moieties in crystalline HOF-25-Ni. With the aid of [Ru(bpy)3 ]2+ and triisopropanolamine, 10 wt% HOF-25-Ni NSs dispersed on graphene oxide efficiently promotes visible-light-driven CO2 reduction, showing a 96.3 % CO selectivity with a prominent conversion rate up to 24 323 µmol g-1 h-1 .

Regulation of a Porphyrin Derivative Containing Two Symmetric Benzoic Acids by Different Pyridines.

A porphyrin derivative called 5,15-di(4-carboxyphenyl)porphyrin (H2DCPp) with carboxyl groups successfully self-assembled on a highly oriented pyrolytic graphite (HOPG) surface and its co-assembly structures with three kinds of pyridine molecules were investigated by scanning tunneling microscopy (STM) with atomic resolution. H2DCPp arranged in a long-range ordered structure, and both 1,4-bis (pyridin-4-ylethynyl) benzene (BisPy), 4,4'-bipyridine (BP) and 1,3,5-tris(pyridin-4-ylethynyl) benzene (TPYB) molecules successfully regulated the host molecules as guest molecules. The well-organized model optimized by density functional theory (DFT) calculations reveals the detailed behavior of the assembly characteristics and regulation of porphyrin derivatives, which is helpful for the research and development of solar cells and nanodevices.

π-Conjugated Macrocycle Host-Guest Coassembly with C60 on HOPG.

Two kinds of π-conjugated macrocycles with aggregation-induced emission (AIE) properties were investigated by scanning tunneling microscopy (STM) to elucidate their self-assembly behaviors and interaction with C60 on a highly oriented pyrolytic graphite (HOPG) surface. Both TPEMC and TPEMCS could self-assemble into orderly cavity structures. However, C60 guest molecules could only successfully enter the cavity of TPEMC to form a stable TPEMC + C60 host-guest coassembly structure. Density functional theory (DFT) calculations were also used to interpret the assembly mechanisms. This work disclosed the assembly characteristic of these new types of conjugated macrocyclic compounds, which was helpful to develop new structural porous luminescent materials.

Controlled Construction of an Exquisite Three-Component Co-assembly Supramolecular Structure at the Liquid-Solid Interface.

A three-component supramolecular co-assembly structure formed at the liquid-solid interface by employing a shape-persistent π-conjugated macrocycle (16mer) and two guest molecules (COR and C60) is demonstrated. Scanning tunneling microscopy (STM) observations revealed that 16mer can serve as a versatile host molecule that can co-assemble with both COR and C60 guest molecules to form stable two-component structures, where the COR guest molecule filled in the gap between the side chains of adjacent 16mer molecules, and the C60 guest molecule entered the inner cavity of 16mer. It was found that the adding sequence of COR and C60 guest molecules is crucial to the resulting co-adsorption structure in the three-component system. To obtain the intriguing 16mer-COR-C60 three-component co-assembly structure, the 16mer and COR two-component co-assembly structure should first be constructed on a HOPG surface, followed by addition of C60. Based on the analysis of the STM results and the density functional theory (DFT) calculations, the formation mechanism of the assembled structures was revealed.

On-Surface Self-Assembled Structural Transformation Induced by Schiff Base Reaction and Hydrogen bonds.

By utilizing scanning tunneling microscopy (STM), the self-assembled nanostructures of three characteristic aldehydes have been examined at the solution-solid interface. By introducing the active reactant 5-aminoisophthalic acid (5-AIPA), we succeeded in changing the self-assembled molecular structures through the condensation reaction and obtained the information on structural transformation in real time. The corresponding carboxyl conjugated derivatives were formed in situ and developed into the closely packed and ordered molecular architectures via hydrogen bonds at the solution-solid surface. The relevant simulations have been utilized to interpret the mechanisms of forming the nanostructures. The corresponding theoretical calculation is used to explain the reaction mechanism. Compared with the traditional ways, the on-surface condensation reaction in situ could not only provide a more convenient method for regulating the self-assembled architectures but also offer a promising strategy for building functional nanostructures and devices.

Progress in self-assemblies of macrocycles at the liquid/solid interface.

Macrocyclic self-assemblies have gained great interest for diversified structures and potential applications, such as catalysis, magnetism, photovoltaic devices, organic light-emitting diodes. Macrocycles can present regular assembly systems at the liquid/solid interface due to theπ-conjugated structures. Furthermore, suitable guest molecules can be selected for constructing multi-component supramolecular co-assemblies. This review mainly summarizes macrocyclic self-assembly structures with different shapes in recent years. All of the studies are completed with the assistance of scanning tunneling microscope at the liquid/solid interface.

Solvent-Dependent Self-Assemblies and Pyridine Modulation of a Porphyrin Molecule at Liquid/Solid Interfaces.

On the highly oriented pyrolytic graphite (HOPG) surface, a new porphyrin molecule MT-4 containing a porphine core with six alkyl chains and two carboxyl groups has been explored using scanning tunneling microscopy (STM) technology. Solvent and pyridine regulation have been proved to be two effective ways to control and tune the supramolecular structure of MT-4 at interfaces. Different high-resolution STM (HR-STM) images with highly ordered and closely packed arrangements were gained at the corresponding liquid-solid interface, including phenyl octane (PO), 1-heptanoic acid (HA), and 1-hexanol. Except for the solvent effect, introducing pyridine derivatives such as 4,4'-vinylenedipyridine (DPE) and 4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene) bis(ethene-2,1-diyl)) dipyridine (PEBP-C8) is also effective to modulate the self-assembly of MT-4. With careful analysis of the STM pictures and the density functional theory (DFT) computational exploration, we figured out the molecular model, interaction energies, and self-assembly mechanism of each system at the interface. This work provides a simple and effective approach for quickly building diverse nanoarchitectures by utilizing different noncovalent interactions. Meanwhile, it would give a perspective to regulate and control self-assembly arrays for devising novel molecular-based materials through more optimal strategies.

Solvent-Dependent Core-Modified Rubyrin Self-Assembly at Liquid/Solid Interfaces.

Scanning tunneling microscopy (STM) was utilized to disclose four novel core-modified rubyrin self-assembly behaviors on the highly-oriented pyrolytic graphite (HOPG) surface, of which N2S4-OR(1)/N2Se4-OR(2) had no phenanthrene pyrrole ring and N2S4-OR(3)/N2Se4-OR(4) had phenanthrene-fused pyrrole rings and meso-aryl substituents. It was discovered that the core-modified rubyrin could self-assemble into either face-on or edge-on monolayer structures selectively at the liquid/HOPG interface in different solvents. There was an obvious solvent-dependent self-assembly for N2S4-OR(3)/N2Se4-OR(4), which adopted an edge-on and face-on structure in 1-phenyloctane and 1-heptanoic acid solvents, respectively, whereas N2S4-OR(1)/N2Se4-OR(2) showed no obvious difference in the assembly structure, which both adopted a face-on structure in the two solvents. Density functional theory (DFT) calculations were also utilized to reveal the relevant self-assembly mechanisms. This study shows a typical solvent effect regulating core-modified rubyrin self-assembly, which is essential for porphyrin-based functional devices' design and manufacture.

Dynamic surface-assisted assembly behaviours mediated by external stimuli.

Supramolecular self-assembly behaviors on solid substrates have been widely investigated in the last few decades. Owing to the complexity of interfacial assembly systems, the precise regulation of supramolecular nanostructures is still challenging and waits to be solved. The supramolecular nanostructures are governed by non-covalent bonds, so they can be disrupted and influenced by an external environment. In this review, the dynamic supramolecular nanostructures that are mediated by external stimuli containing guest species, light irradiation, temperature and electric field are discussed in detail. The research studies mentioned in this article are all accomplished by STM, and the effects of these external stimuli on the assembled nanostructures have been elucidated exhaustively here.

A Scalable General Synthetic Approach toward Ultrathin Imine-Linked Two-Dimensional Covalent Organic Framework Nanosheets for Photocatalytic CO2 Reduction.

Fabricating ultrathin two-dimensional (2D) covalent organic framework (COF) nanosheets (NSs) in large scale and high yield still remains a great challenge. This limits the exploration of the unique functionalities and wide range of application potentials of such materials. Herein, we develop a scalable general bottom-up approach to facilely synthesize ultrathin (<2.1 nm) imine-based 2D COF NSs (including COF-366 NSs, COF-367 NSs, COF-367-Co NSs, TAPB-PDA COF NSs, and TAPB-BPDA COF NSs) in large scale (>100 mg) and high yield (>55%), via an imine-exchange synthesis strategy through adding large excess amounts of 2,4,6-trimethylbenzaldehyde into the reaction system under solvothermal conditions. Impressively, visualization of the periodic pore lattice for COF-367 NSs by a scanning tunneling microscope (STM) clearly discloses the ultrathin 2D COF nature. In particular, the ultrathin COF-367-Co NSs isolated are subject to the heterogeneous photocatalyst for CO2-to-CO conversion, showing excellent efficiency with a CO production rate as high as 10 162 µmol g-1 h-1 and a selectivity of ca. 78% in aqueous media under visible-light irradiation, far superior to corresponding bulk materials and comparable with the thus far reported state-of-the-art visible-light driven heterocatalysts.

Selective Adsorption of C60 in the Supramolecular Nanopatterns of Donor-Acceptor Porphyrin Derivatives.

The nanostructure of active layers consisting of donor and acceptor molecules is responsible for the separation and transfer processes of charge carriers, which may result in different photoelectric conversion efficiencies of organic photovoltaic cells (OPVCs). Therefore, intensive study on the relationships among nanostructures, intermolecular interactions, and molecular chemical skeletons is necessary for preparing controlled nanostructures of active layers by designing photovoltaic molecules. In this research, the self-assembled nanopatterns of three (DPP-ZnP-E)2-based molecules on highly oriented pyrolytic graphite surface were probed by scanning tunneling microscopy and analyzed by density functional theory calculations. The results indicated that different bridges, diethynylene, diethynylene-dithienyl, and diethynylene-phenylene, in (DPP-ZnP-E)2-based molecules not only made a difference to intermolecular interactions and cooperated with molecule-substrate interactions, consequently affecting the packed nanopattern, but also influenced the adsorption of fullerene acceptors in the nanopatterns of (DPP-ZnP-E)2-based molecules. C60 molecules were found to be selectively adsorbed atop the dithienyl groups of (DPP-ZnP-E)2-2T donor molecules probably by S···π interactions compared with (DPP-ZnP-E)2 or (DPP-ZnP-E)2-Ph molecules. This study on the assembled nanopatterns of the three (DPP-ZnP-E)2-based molecules would be conductive to (DPP-ZnP-E)2-based optoelectronic materials design in OPVCs.

Temperature-Triggered Self-Assembled Structural Transformation: From Pure Hydrogen-Bonding Quadrilateral Nanonetwork to Trihexagonal Structures.

Adequate control over the structures of molecular building blocks plays an important role in the fabrication of desired supramolecular nanostructures at interfaces. In this study, the formation of a pure hydrogen-bonding co-assembly supramolecular nanonetwork on a highly oriented pyrolytic graphite surface was demonstrated by means of a scanning tunneling microscope. The thermal annealing process was conducted to monitor the temperature-triggered structural transformation of the self-assembled nanonetwork. On the basis of the single-molecule-level resolution scanning tunneling microscopy images, together with the density functional theory calculations, the formation mechanisms of the formed nanoarrays were proposed. The results have great significance with regard to controlled construction of complex nanostructures on the surface.

Bilayer Adsorption of Porphyrin Molecules Substituted with Carboxylic Acid atop the NN4A Network Revealed by STM and DFT.

Bottom-up technology is a bridge connecting a two-dimensional (2D) monolayer structure with a three-dimensional (3D) bulk structure. From 2D to 3D, it helps us to understand the driving force of an organization process to control the molecular arrangement in the 3D phase. Here, we aimed at the fabrication of multilayer nanostructures on solid substrates. Bis(3,5-diacidic)diazobenzene (NN4A) was chosen as one molecule because of its photosensitive azo group and carboxylic group possessing hydrogen bonding effect, while porphyrin molecules composed of different numbers and positions of carboxylic acid groups were used as the other component. It was found that the porphyrin molecules could adopt different adsorption configurations because of the influence of carboxylic groups, leading to different subsequent coassemblies on the solid surface. The NN4A/porphyrin systems underwent structural transformation when NN4A molecules were adsorbed on the highly oriented pyrolytic graphite surface with predeposited porphyrin. This work displayed an efficient method on the construction of multilayer nanostructures in the molecular surface engineering and provided a new way to construct 3D structures based on the molecular design.

On-Surface Crystallization Behaviors of H-Bond Donor-Acceptor Complexes at Liquid/Solid Interfaces.

Two-dimensional (2D) crystallization behaviors of A-TPC n ( n = 4, 6, 10), T3C4, and hydrogen-bonded complexes T3C4@TPC n ( n = 4, 6, 10) are investigated by means of scanning tunneling microscope (STM) observations and density functional theory (DFT) calculations. The STM observations reveal that A-TPC4, A-TPC10, and T3C4 self-organize into dumbbell-shaped structures, well-ordered bright arrays, and zigzag structures, respectively. Interestingly, T3C4@TPC10 fails to form the cage-ball structure, whereas T3C4@TPC4 and T3C4@TPC6 co-assemble into cage-ball structures with the same lattice parameters. The filling rates of the balls of these two kinds of cage-ball structures depend heavily on the deposition sequence. As a result, the filling rates of the cages in T3C4/A-TPC n ( n = 4, 6) with deposition of T3C4 anterior to A-TPC n are higher than those in A-TPC n/T3C4 ( n = 4, 6) with the opposite deposition sequence. Furthermore, lattice defects formed by T3C4 coexist with the cage-ball structures. Moreover, the similar energy per unit area of lattice defects (-0.101 kcal mol-1 Å-2) and the two cage-ball networks (-0.194 and -0.208 kcal mol-1 Å-2, respectively), illustrating the similar stabilities of lattice defects and cage-ball networks, demonstrates the rationality of lattice defects. Combining STM investigations and DFT calculations, this work could provide a useful approach to investigate the 2D crystallization mechanisms of supramolecular liquid crystals on surfaces.