Self-assembly of bipyridine derivatives at solid/liquid interface: Effects of the number of peripheral alkyl chains and metal coordination on the two-dimensional structures

Self-assembled two-dimensional structures of bipyridine derivatives (bpys) were observed by scanning tunneling microscopy at HOPG/1-phenyloctane interface. Two types of bpy molecules were used in this study. One is bpy 1, which has two alkyl chains on each end, and the other is bpy 2, which holds single alkyl chain on each end. The bpy 1 formed a monolayer, which is composed of a bent molecular structure with interdigitated alkyl chains. In the case of bpy 2, the structure exhibited pm plane group symmetry. A pair of molecules formed a columnar structure, and the alkyl chains aligned in a tail-to-tail orientation. Metal coordination of both bpy samples increased the intermolecular distance at the π-conjugated units, resulting in the formation of lamellar structure. Although both bpys showed straight form, the alkyl chain unit of complexed bpy 1 was not interdigitated, whereas that of complexed bpy 2 was interdigitated. Thus, the metal–metal distances could be tuned by changing the number of alkyl chain unit.