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The hierarchical organization of building blocks is an important characteristic of self-assembly. Herein, we report a series of triangular hierarchical assemblies formed by C3-symmetric 5,10,15-triethyl-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazole-2,7,12-tricarbaldehyde (M1) on the graphite surface. The molecule assembles into a hexagonal array on the graphite surface at room temperature with a trimeric assembly motif as the basic building block of the hierarchical assembly. With the increase of annealing temperature, the sizes of triangles in hierarchical assemblies vary from large to small with the presence of antiparallelly arranged molecular dimers as building blocks at the triangular boundaries. The hierarchical-order-level-dependent intermolecular interaction and molecule–substrate interaction were modeled, and the entropy contributions of alkyl substitution at different temperatures were proposed to account for the observed structural evolution process. This work provides a new example of hier...

The on-surface coupling reactions of terminal alkynes catalyzed by exogenous cupric ions on chemically inert highly oriented pyrolytic graphite (HOPG) surface have been investigated by scanning tunnelling microscopy. In the presence of exogenous cupric ions, diyne-linked nanostructures generated via homocoupling of terminal alkynes are the exclusive products, whereas no coupling reaction occurs for the terminal alkynes on the surface in the absence of the cupric ions, suggesting that exogenous cupric ions are efficient to catalyze the highly chemoselective on-surface reaction of terminal alkynes. The HOPG surface displays a template effect to the growth and alignment of the products on the surface. As a result, 2D arrays of diyne-linked zigzag polymers and 2D diyne-linked porous polymers are fabricated from ditopic monomer 3,6-diethynylcarbazole and tritopic monomer 1,3,5-tris-(4-ethynylphenyl) benzene, respectively. This synthetic strategy combining the high selectivity of cupric ion catalyst as well as the template effect of on-surface synthesis approach could be a general strategy to fabricate diyne-linked nanostructures and nanomaterials on solid surfaces.

The on-surface synthesis of single-layered covalent organic frameworks (sCOFs) has been investigated by employing a 3-fold symmetric monomer 1 carrying aldehyde groups and the ditopic diamine building block 2 on a highly oriented pyrolytic graphite surface. The self-assembly of molecule 1 is persistently observed at the stoichiometric ratio of the reactive groups. The growth of sCOF network is observed, however, only at the excess of diamine monomers. By investigating the growth process of the sCOF network, the role of excessive diamine monomers can be understood by two aspects. Increasing the molar ratio of diamine monomer provides the driving force for the structural transition from the monomer self-assembly to the formation of the sCOF network. On the other hand, the excess diamine monomers provide basic environment for the transimination reaction and promote the formation of highly ordered sCOFs. The present work provides molecular understanding of the role of transimination reaction in imine-based COF synthesis.

We have studied the self-assembly structure of meso-diphenyltetrathia [22]-annulene [2,1,2,1] (DPTTA) on highly oriented pyrolytic graphite (HOPG), Au(111), and single-layer graphene (SLG) modified Au(111) substrates. High resolution scanning tunneling microscopy (STM) reveals that DPTTA molecules pack into one dimensionally ordered row structure on graphene and HOPG surfaces, while assemble into two dimensional close-packed structure on Au(111) surface. We ascribe this difference to the effect of the substrate. The addition of C60 molecules on these DPTTA modified substrates further reveals that the structural difference in DPTTA adlayer can affect its ability to form donor-acceptor (D-A) hierarchical structure with C60 molecules. The results provide an example of substrate effect in self-assemblies of functional molecules, which is significant for the design of molecular based devices.

The design and construction of stable porous networks featuring tunable cavities for selective guest inclusion remains a great challenge in construction of functional miniature devices. Herein we report on construction and guest inclusion of stable 2D porphyrin-based molecular square grids connected by imine bonds showing crystalline pattern with periodic square cavities. Diperylene diimides molecules can be decorated into the square pores of the porphyrin-based molecular template on HOPG surfaces. The periodicity control over the covalent molecular grid and thus that of guest molecules is demonstrated by changing the building block. The preparation of robust host–guest systems may facilitate the fabrication of molecular miniature devices with designable properties.

A bilayer covalent organic framework (COF) of TTF-based building blocks was obtained by imine reaction between tetrathiafulvalene tetraaldehyde (4ATTF) and p-phenylenediamine (PPDA). Direct evidence for the eclipsed stacking of bilayer structure via π-π interaction between TTF units is provided by high resolution scanning tunneling microscopy.

We combine chiral amplification and host–guest chemistry to demonstrate an approach to achieve a switchable chiral assembly. After the addition of the guest coronene, homochiral honeycomb patterns transform into host–guest sunflower structures, in which supramolecular chirality is modulated dramatically.

We systematically studied the operation of coadsorber-induced surface chirality in a series of enantiomeric surface supramolecular assemblies. The correlation of chiral amplification degree with the proportion of enantiomeric interaction in the total intermolecular interaction is deduced.

The orthogonality between the Schiff base reaction and the boronic acid dehydration reaction is explored during the on-surface synthesis process., The orthogonality between the Schiff base reaction and the boronic acid dehydration reaction is explored during the on-surface synthesis process. By activating the above two reactions in one-step and employing asymmetrical substituted monomers and the 3-fold symmetric monomer 1,3,5-tris(4-aminophenyl)benzene (TAPB), highly ordered imine–boroxine hybrid single-layered covalent organic frameworks (sCOFs) have been successfully constructed on HOPG by a gas–solid interface reaction method and characterized by scanning tunnelling microscopy (STM). In particular, the reaction between the meta-substituted monomer and TAPB generates sCOFB with a windmill structure, which is the first sCOF with surface chirality so far reported. The demonstration of the one-step synthesis of multiple linkages to form sCOFs can further enlarge the sCOF family and expand the design routes for functional 2D organic nanomaterials.