Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks

The electronic properties of 2D boroxine networks are computationally investigated by simulating the NEXAFS spectra of a series of molecular models, with or without morphologic defects, with respect to the ideal honeycomb structure. The models represent portions of an irregular 2D boroxine framework obtained experimentally, as supported by the Au(111) surface. The B K-edge NEXAFS spectra are calculated within the transition potential (TP) approximation (DFT-TP). The role of the Au(111) supporting surface on the spectral features has also been investigated by comparing the calculated spectra of a defect-rich model in its free-standing and supported form. The calculated NEXAFS spectra differ from the experimental ones, as the position of the main resonance does not match in the two cases. This finding could suggest the presence of a strong interaction of the 2D boroxine network with the Au substrate, which is not captured in the model calculations. However, good agreement between measured and calculated B K-edge NEXAFS spectra is obtained for a model system, namely, trihydroxy boroxine, in which the B atoms are less screened by the valence electrons compared to the B-B linked boroxine network models considered here. These results suggest catalytic activity in the gold substrate in promoting a weakening or even the breaking of the B-B bond, which is not revealed by calculations.