Supramolecular self-assembled polynuclear complexes from tritopic, tetratopic, and pentatopic ligands: Structural, magnetic and surface studies

Polymetallic, highly organized molecular architectures can be created by bottom-up self-assembly methods using ligands with appropriately programmed coordination information. Ligands based on 2,6-picolyldihydrazone (tritopic and pentatopic) and 3,6-pyridazinedihydrazone (tetratopic) cores, with tridentate coordination pockets, are highly specific and lead to the efficient self-assembly of square [3 x 3] Mn-9, [4 x 4] Mn-16, and [5 x 5] Mn-25 nanoscale grids. Subtle changes in the tritopic ligand composition to include bulky end groups can lead to a rectangular 3 x [1 x 3] Mn-9 grid, while changing the central pyridazine to a more sterically demanding pyrazole leads to simple dinuclear copper complexes, despite the potential for binding four metal ions. The creation of all bidentate sites in a tetratopic pyridazine ligand leads to a dramatically different spiral Mn-4 strand. Single-crystal X-ray structural data show metallic connectivity through both mu-O and mu-NN bridges, which leads to dominant intramolecular antiferromagnetic spin exchange in all cases. Surface depositions of the Mn-9, Mn-16, and Mn-25 square grid molecules on graphite (HOPG) have been examined using STM/CITS imagery (scanning tunneling microscopy/current imaging tunneling spectroccopy), where tunneling through the metal d-orbital-based HOMO levels reveals the metal ion positions. CITS imagery of the grids clearly shows the presence of 9, 16, and 25 manganese ions in the expected square grid arrangements, highlighting the importance and power of this technique in establishing the molecular nature of the surface adsorbed species. Nanoscale, electronically functional, polymetallic assemblies of this sort, created by such a bottom-up synthetic approach, constitute important components for advanced molecule-based materials.