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.