Fabrication of bilayer tetrathiafulvalene integrated surface covalent organic frameworks.

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.

Substrate Orientation Effect in the On-Surface Synthesis of Tetrathiafulvalene-Integrated Single-Layer Covalent Organic Frameworks.

The on-surface reactions of tetrathiafulvalene equipped with four benzaldehyde groups (4ATTF) and ditopic diamine molecules are investigated. 4ATTF tends to form large-scale-ordered rhombus structures when reacted with p-phenylenediamine (PPDA). A longer ditopic diamine molecule, 1,1'-biphenyl-4,4'-diamine dihydrochloride (BPDA), causes the domain size of the regular rhombus structure to decrease and triangular and irregular rhombus structures to appear upon reaction with 4ATTF. However, in the rhombus structures formed by different-length ditopic diamine molecules, the single-layer covalent organic frameworks on the graphite surface preferentially orient in alignment with the underlying HOPG substrate lattice.

Electrostatic-interaction-induced molecular deposition of a hybrid bilayer on Au(111): a scanning tunneling microscopy study.

Hybrid bilayers consisting of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and meso-tetra(4-pyridyl)porphine (TPyP) have been successfully constructed on Au(111) and investigated by electrochemical scanning tunneling microscopy (ECSTM). Under the guidance of the electrostatic interaction between negatively charged sulfonate groups and positively charged pyridyl groups, the underlying HPTS arrays act as templates for the deposition of cationic TPyPs, forming two types of TPyP/HPTS complex bilayers. The present work provides a feasible way to fabricate hybrid multilayers on the electrode surface via electrostatic interaction, which has great significance for the design of molecular nanodevices.

Directed assembly of fullerene on modified Au(111) electrodes.

Here we show a conceptual approach to realize the scanning tunneling microscopy based induced-assembly of fullerene (C60) molecules on top of a buffer organic adlayer at room temperature in a solution environment. The realization of spatially-defined C60 assembly is attributed to the modulation of substrate-molecular interactions with the assistance of a buffer layer.

Simultaneous construction of two linkages for the on-surface synthesis of imine-boroxine hybrid covalent organic frameworks.

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.