Two-dimensional Kondo array of phthalocyanine-porphyrin bimolecular self-assembled systems

Kondo effect offers an important paradigm to understand strongly correlated many-body physics. Metal-phthalocyanines and metal-porphyrins provide versatile platforms for investigating Kondo effect benefiting from diverse ranges of central metal ions with different magnetic states. Here, we report the two-dimensional (2D) Kondo array of bimolecular self-assembly networks composed of iron-phthalocyanine (FePc) and iron-chiral-porphyrin (named as $\mathrm{Fe}c{\mathrm{F}}_{16}\mathrm{TPP}$) molecules. We have successfully realized the on-surface synthesis of hydrogen-bonds-connected FePc-$\mathrm{Fe}c{\mathrm{F}}_{16}\mathrm{TPP}$ checkerboard framework on Au(111). In this network, both FePc and $\mathrm{Fe}c{\mathrm{F}}_{16}\mathrm{TPP}$ molecules display Kondo resonance near Fermi level and exhibit $({d}_{{z}^{2}}^{2}{d}_{\ensuremath{\pi}}^{2})$ electronic configuration. First-principles calculations revealed that the intermolecular interaction play a vital role in modulating the symmetry of the network and the spin states of molecules. Furthermore, we have predicted that by substituting the outmost fluorine atoms with hydrogen atoms in $\mathrm{Fe}c{\mathrm{F}}_{16}\mathrm{TPP}$, a striped network consisting of FePc and $\mathrm{Fe}c\mathrm{TPP}$ molecules forms. The $\mathrm{F}{\mathrm{e}}^{2+}$ ions in $\mathrm{FePc}\text{\ensuremath{-}}\mathrm{Fe}c\mathrm{TPP}$ striped network exhibit $({d}_{{z}^{2}}^{1}{d}_{\ensuremath{\pi}}^{3})$ state, as determined through the first-principles calculations. Our work combines supramolecular chemistry for engineering the Kondo arrays and coordination chemistry for their manipulation.