Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms

The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π-d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal-organic trimer, in which three HATP molecules were coordinated by Cu₃ clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)-Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal-organic bonds.