André's Paper in ZAAC is one of the most read papers in ZAAC
André's Paper "Synthesis and crystal structures of rhodium acetate paddle-wheel complexes with anchor group-functionalised and hydrogen bond-supported axial ligands" appeared in August of 2022. Almost two years later, it belongs to ZAAC's most downloaded papers
André's paper reports on the synthesis and X-ray structures of four Rh2(OAc)4(LAx)2 paddle-wheel complexes with methylthio-modified axial ligands derived from benzamidine, anilinopyrimidine, or isothiourea. These complexes are capable of forming N−H⋅⋅⋅O hydrogen bonds to the equatorially bridging acetate ligands. This design aims to suppress the dissociation of the axial ligands and enhance their suitability for single-molecule conductance measurements using a scanning tunneling microscope break-junction (STM-BJ) setup. This research presents the characteristic spectroscopic features, including NMR, IR, and visible spectra, as well as the crystal structures and hydrogen-bonding motifs of these complexes. Additionally, a DFT-based screening of their frontier molecular orbitals indicates that hydrogen-bonding stabilizes axial ligand binding by 15 to 30 kJ/mol. The HOMO of the rhodium paddle-wheels is found to be closer to the Au work function than the LUMO, suggesting that these complexes function as hole conductors. If you are intereested in learning more, click here.