In-Plane Hydrogen Bonds and Out-of-Plane Dipolar Interactions in Self-Assembled Melem Networks

Melem(2,6,10-triamino-s-heptazine) is the building block of melon,a carbon nitride (CN) polymer that is proven to produce H2 from water under visible illumination. With the aim of bringing additional insight into the electronic structure of CN materials, we performed a spectroscopic characterization of gas-phase melem and of a melem-based self-assembled 2D H-bonded layer on Au(111) by means of ultraviolet and X-ray photoemission spectroscopy (UPS, XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, we performed density functional theory (DFT) simulations of the same systems to unravel the molecular charge density redistribution caused by the in-plane H-bonds. Comparing the experimental results with the spectroscopic DFT simulations, we can correlate the induced charge accumulation on the N-amino atoms to the red-shift of the corresponding N 1s binding energy (BE) and of the N-amino 1s -> LUMO+n transitions. Moreover, when introducing a supporting Au(111) surface in the computational simulations, we observe a molecule-substrate interaction that almost exclusively involves the out-of-plane molecular orbitals, leaving those engaged in the in-plane H-bonded network rather unperturbed.