Formation of heterocaryotic and homonuclear bridged–dimeric complexes on surface

The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris(10-carboxydecyloxy)benzene (TCDB) template through scanning tunneling microscopy (STM). STM images of molecular adlayers of zinc tetraphenylporphyrin (ZnTPP), zinc phthalocyanine (ZnPc), and their mixture are reported. ZnTPP and ZnPc can spontaneously form highly an ordered structure with a 1:1 molar ratio, which is different from that of individual ZnPc. The coordinated bimolecular complexes bridged with axial ligands, simply as ZnPc–DPP–ZnTPP and ZnPc–DPE–ZnPc, are presented and the corresponding surface structures are compared. ZnPc and ZnTPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the ZnPc–DPE–ZnPc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.

Graphical abstractWe have observed heterocaryotic and homonuclear dimeric complexes of ZnTPP–ZnPc and ZnPc–ZnPc bridged by axial ligands DPP and DPE in a template of TCDB on HOPG surface by means of scanning tunneling microscopy (STM).Figure optionsDownload full-size imageDownload as PowerPoint slide