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 FecF16TPP) molecules. We have successfully realized the on-surface synthesis of hydrogen-bonds-connected FePc-FecF16TPP checkerboard framework on Au(111). In this network, both FePc and FecF16TPP molecules display Kondo resonance near Fermi level and exhibit (dz22dπ2) 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 FecF16TPP, a striped network consisting of FePc and FecTPP molecules forms. The Fe2+ ions in FePc-FecTPP striped network exhibit (dz21dπ3) state, as determined through the first-principles calculations. Our work combines supramolecular chemistry for engineering the Kondo arrays and coordination chemistry for their manipulation.