Ultraprecise templating on the sub-5 nm scale is one of the attractive features of two-dimensional networks on surfaces. Mostly demonstrated for molecular guest species in ultrahigh vacuum experiments and at the liquid-solid interface [1], network controlled deposition in an electrochemical environment has, so far, been limited to the intercalation of metal monolayers at the interface between nanoislands of thiols corralled by a network and the underlying substrate [2,3].However, extending electrodeposition of metal monolayers to empty network pores is of interest due to the catalytic properties of metallic nanostructures as well as the possibility of orthogonal self-assembly of molecules through tailoring of molecule-substrate interactions.Here we present results on the underpotential deposition (UPD) of Cu templated by a supramolecular honeycomb network. Consisting of 3,4:9,10-perylenetetracarboxylic diimide (PTCDI) and melamine, the network is, in contrast to a self-assembled monolayer/network hybrid structure [2,3], not sufficiently stable under the acidic environment usually employed in Cu-UPD. However, deposition at higher pH improves the stability of the network to the extent that Cu-UPD becomes feasible. Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) show that the network structure is preserved upon metal UPD and that the UPD is confined to the pore area. Atomically resolved STM images of anions adsorbed on the UPD islands and on uniform UPD layers exhibit significant differences in height contrast, thus, indicating an influence of the network confinement on the structure of the UPD layer.[1] T. Kudernac, S. B. Lei, J. Elemans, and S. De Feyter, Chem. Soc. Rev. 38, 402-21 (2009).[2] R. Madueno, M. T. R�is�nen, C. Silien, M. Buck, Nature 454, 618 (2008).[3] C. Silien, M. T. R�is�nen, M. Buck, Small 6, 394 (2010).

Cu underpotential deposition on Au(111) confined by a hydrogen bonded network

247th National Meeting (2014)

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