Pyridine-induced interfacial structural transformation of tetraphenylethylene derivatives investigated by scanning tunneling microscopy

The two-dimensional self-assembly behaviors of tetraphenylethylene (TPE) molecules are significant for further applications, but reports are rare. The self-assembled structures of two C₂-symmetry TPE derivatives (H₄TCPE and H₄ETTC) possessing propeller structures and their stimulus responses to the addition of vinylpyridine derivatives were thoroughly studied with the assistance of scanning tunneling microscopy (STM) technique in combination with density functional theory (DFT) calculations. Although their chemical structures were similar, the H₄TCPE and H₄ETTC molecules self-assembled into closely packed lamellar and quadrilateral structures, respectively, at the 1-heptanoic acid/HOPG interface. After the addition of pyridine derivatives (DPE, PEBP-C4, and PEBP-C8), H₄TCPE and H₄ETTC showed different responsiveness resulting in different co-assembly structures. The results indicated that the structures of pyridine derivatives—including backbones and substituents—affected the intermolecular interactions of both H₄TCPE/pyridine and H₄ETTC/pyridine systems. The modification of the self-assembly behaviors of propeller-shaped H₄TCPE and H₄ETTC would contribute to the construction of more complex multilevel nanostructures.