Citation:
Queck , F , Krejčí , O , Scheuerer , P , Bolland , F , Otyepka , M , Jelínek , P & Repp , J 2018 , ' Bonding Motifs in Metal-Organic Compounds on Surfaces ' , Journal of the American Chemical Society , vol. 140 , 40 , pp. 12884−12889 . https://doi.org/10.1021/jacs.8b06765
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Abstract:
The bonds in metal organic networks on surfaces govern the resulting geometry as well as the electronic properties. Here, we study the nature of these bonds by forming phenazine-copper complexes on a copper surface by means of atomic manipulation. The structures are characterized by a combination of scanning probe microscopy and density functional theory calculations. We observed an increase of the molecule-substrate distance upon covalent bond formation and an out-of-plane geometry that is in direct contradiction with the common expectation that these networks are steered by coordination bonds. Instead, we find that a complex energy balance of hybridization with the substrate, inhomogeneous Pauli repulsion, and elastic deformation drives the phenazine-copper interaction. Most remarkably, this attractive interaction is not driven by electron acceptor properties of copper but is of completely different donation/back-donation mechanism between molecular π-like orbitals and sp-like metal states. Our findings show that the nature of bonds between constituents adsorbed on surfaces does not have to follow the common categories.
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