Density Functional Theory Analysis of Carboxylate-Bridged Diiron Units in Two-Dimensional Metal−Organic Grids

Carboxylate-bridged diiron units have been realized recently in two dimensions via metal-directed self-assembly of simple organic linkers. They represent notably a coupling motif stabilizing a series of nanoporous metal-organic coordination networks and are reminiscent of catalytically active sites in metalloproteins. To rationalize their atomic structure, chemical bonding, and electronic properties, we performed density functional theory calculations for exemplary Fe-terephthalate grids assembled on the Cu(100) surface. The obtained atomistic description and understanding is decisive for the considerate use of two-dimensional metal-organic coordination networks as templates, guest systems, or catalysts.