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Supramolecular Nanostructuring of Silver Surfaces via Self‐Assembly of [60]Fullerene and Porphyrin Modules
Author(s) -
Bonifazi D.,
Kiebele A.,
Stöhr M.,
Cheng F.,
Jung T.,
Diederich F.,
Spillmann H.
Publication year - 2007
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200600586
Subject(s) - porphyrin , materials science , fullerene , supramolecular chemistry , scanning tunneling microscope , monolayer , molecule , self assembly , nanotechnology , crystallography , photochemistry , chemistry , organic chemistry
Recent achievements in our laboratory toward the “bottom‐up” fabrication of addressable multicomponent molecular entities obtained by self‐assembly of C 60 and porphyrins on Ag(100) and Ag(111) surfaces are described. Scanning tunneling microscopy (STM) studies on ad‐layers constituting monomeric and triply linked porphyrin modules showed that the molecules self‐organize into ordered supramolecular assemblies, the ordering of which is controlled by the porphyrin chemical structure, the metal substrate, and the surface coverage. Specifically, the successful preparation of unprecedented two‐dimensional porphyrin‐based assemblies featuring regular pores on Ag(111) surfaces has been achieved. Subsequent co‐deposition of C 60 molecules on top of the porphyrin monolayers results in selective self‐organization into ordered molecular hybrid bilayers, the organization of which is driven by both fullerene coverage and porphyrin structure. In all‐ordered fullerene–porphyrin assemblies, the C 60 guests organize, unusually, into long chains and/or two‐dimensional arrays. Furthermore, sublimation of C 60 on top of the porous porphyrin network reveals the selective long‐range inclusion of the fullerene guests within the hosting cavities. The observed mode of the C 60 self‐assembly originates from a delicate equilibrium between substrate–molecule and molecule–molecule interactions involving charge‐transfer processes and conformational reorganizations as a consequence of the structural adaptation of the fullerene–porphyrin bilayer.