Visualizing Improved Spin Coupling in Large Magnetic Molecules

In an attempt to combine a high spin ground state and a large magnetic anisotropy in one molecule, triplesalen-based complexes are promising building blocks for a new generation of single molecule magnets (SMMs). The spin coupling in these molecules is based on the spin polarization effect, which requires a delocalized aromatic $\pi$-system in the central carbon ring of the complex. Unfortunately, chemical analysis indicates that this ring can change its configuration to [6]radialene, therefore causing a loss of aromaticity and weakening the magnetic coupling. We have employed a combination of scanning tunneling microscopy (STM) and spectroscopy (STS) to investigate single Cu$_3$-triplesalen and Cu$_3$-triplesalalen molecules, the latter being designed to show an enhanced intramolecular spin coupling. The large molecules were deposited in situ using the unconventional techniques pulse injection and rapid heating. A thorough structural and spectroscopic analysis allows us to discuss the electronic properties of the two complexes, with a special focus on the state of the central carbon ring. We find that even small changes in the ligand structure have a drastic influence on the intramolecular spin coupling, which opens the way for an improved rational design of future SMMs.