Self-assembling in fabrication of ordered porphyrins and phthalocyanines hybrid nano-arrays on HOPG

5,10,15,20-Tetrakis(4-tetradecylphenyl)-porphyrin (P14) has been synthesized and its self-assembling behavior on highly oriented pyrolytic graphite (HOPG) surfaces when coadsorbing with tetradecane molecules have been investigated in this work. Scanning tunneling microscope (STM) studies show that the phthalocyanine (Pc) and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (F16CuPc) can be immobilized by the network formed from P14 and consequently lead to two kinds of well-defined hybrid porphyrins and phthalocyanines hybrid nano-arrays. Interestingly, F16CuPc could form multilayer structure. The theoretical simulation results show that pi-pi stacking interactions and C-H center dot center dot center dot F-C hydrogen bonding between P14 and F16CuPc play a major role in stabilizing the P14/F16CuPc alternating single-/multi-layer architecture.