Intercalation in Layered Metal-Organic Frameworks: Reversible Inclusion of an Extended π-System

We report the synthesis of layered [Zn-2 (bdc)(2)(H2O)(2)] and [Cu-2(bdc)(2)(H2O)(2)] (bdc = benzdicarboxylate) metal organic frameworks (MOF) carried out using the liquid-phase epitaxy approach employing self-assembled monolayer (SAM) modified Au-substrates. We obtain Cu and Zn MOF-2 structures, which have not yet been obtained using conventional, solvothermal synthesis methods. The 2D Cu2+ dimer paddle wheel planes characteristic for the MOF are found to be strictly planar, with the planes oriented perpendicular to the substrate. Intercalation of an organic dye, DXP, leads to a reversible tilting of the planes, demonstrating the huge potential of these surface-anchored MOFs for the intercalation of large, planar molecules.