Supramolecular chemistry holds unique prospects for the fabrication of novel functional materials. Molecularly precisely defined, nanometer-sized subunits which may already be rather complex self-assemble to form even more complex structures which exhibit functionalities not provided by the individual building blocks. In two dimensions, the understanding of a surface-templated assembly of organic molecules (ligands) interacting through hydrogen bonds or ionic interactions has been significantly advanced in recent years.[1]Here we extend the fabrication of surface-anchored networks beyond the formation of planar, two-dimensional adlayers by demonstrating the synthesis of highly-ordered, three-dimensional porous metal-organic frameworks (MOFs) nucleated on organic surfaces using liquid phase epitaxy [2]. The availability of porous frameworks rigidly anchored to solid surfaces opens the prospect of adding additional functionality to these ultrathin surface coatings [4] by placing nanoobjects inside the pores within the MOFs, e.g. metal clusters or dye molecules [3]. We will demonstrate the potential of this approach by loading the three-dimensional porous scaffolds with metal-containing molecules such as ferrocene and then characterizing their properties using electrochemistry.[5] [1] J.V. Barth, Annual Review of Physical Chemistry 58 ,  375 (2007)[2] O. Shekhah, H. Wang, S.Kowarik, F.Schreiber, M.Paulus, M.Tolan, C.Sternemann, F.Evers, D.Zacher, R.A. Fischer, Ch.W�ll, J.Am.Chem.Soc. 129 , 15118 (2007)[3] H.K. Arlsan, O. Shekhah, D.C.F. Wieland, M. Paulus, C. Sternemann, M. A. Schroer, S. Tiemeyer, M. Tolan, R.A. Fischer, Ch. W�ll J. Am. Chem. Soc., 133  (21), 8158-8161 (2011)[4] MOF thin films: existing and future applications, O.Shekhah, J.Liu, R.A.Fischer, Ch.W�ll Chem.Soc.Rev. 40 , 1081 (2011)[5] A.Drag�sser, O. Shekhah, O. Zybaylo, C. Shen, M. Buck, Ch. W�ll, D. Schlettwein, Chem. Comm., 48 , 663 (2012)

Interfacial systems chemistry: Surface-templated assembly of 3D functional frameworks

247th National Meeting (2014)

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