By means of Mn-Cu transmetalation, we incorporated Mn atoms in an array of TCNQ (7,7,8,8-tetracyanoquinodimethane) grown on Cu(100), forming a long range ordered and commensurate metal–organic coordination network (MOCN). Preliminary Sn alloying of the Cu(100) surface allowed us to control the degree of substrate reactivity, thus preventing the chemical interaction of the Mn-TCNQ MOCN with the substrate. Mn2+ ions are stabilized in an artificial tetra-pyrrolic coordination, which mimics the macrocyle configuration of Mn-phthalocyanines/porphyrins. X-ray absorption spectroscopy at the Mn L2,3-edge indicates that the Mn ions are in a high-spin state (S = 5/2), in agreement with DFT + U calculations which also shows that the electronic structure of this Mn-TCNQ MOCN is very similar to that of the corresponding unsupported MOCN.
