The effect of intermolecular H-bonding interactions on the local electronic structure of N-containing functional groups (amino group and pyridine-like N) that are characteristic of polymeric carbon nitride materials p-CN(H), a new class of metal-free organophotocatalysts, was investigated. Specifically, the melamine molecule, a building block of p-CN(H), was characterized by X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The molecule was studied as a noninteracting system in the gas phase and in the solid state within a H-bonded network. With the support of DFT simulations of the spectra, it was found that the H-bonds mainly affect the N 1s level of the amino group, leaving the N 1s level of the pyridine-like N mostly unperturbed. This is responsible for a reduction of the chemical shift between the two XPS N 1s levels relative to free melamine. Consequently, N K-edge NEXAFS resonances involving the amino N 1s level also shift to lower photon energies. Moreover, the solid-state absorption spectra showed significant modification/quenching of resonances related to transitions from the amino N 1s level to σ* orbitals involving the NH2 termini. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Spectroscopic fingerprints of intermolecular H-bonding interactions in carbon nitride model compounds / Lanzilotto, Valeria; Silva, J Luis; Zhang, Teng; Stredansky, Matuš; Grazioli, Cesare; Simonov, Konstantin; Giangrisostomi, Erika; Ovsyannikov, Ruslan; De Simone, Monica; Coreno, Marcello; Araujo, C Moyses; Brena, Barbara; Puglia, Carla. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 24:53(2018), pp. 14198-14206. [10.1002/chem.201802435]
Spectroscopic fingerprints of intermolecular H-bonding interactions in carbon nitride model compounds
Lanzilotto, Valeria
;
2018
Abstract
The effect of intermolecular H-bonding interactions on the local electronic structure of N-containing functional groups (amino group and pyridine-like N) that are characteristic of polymeric carbon nitride materials p-CN(H), a new class of metal-free organophotocatalysts, was investigated. Specifically, the melamine molecule, a building block of p-CN(H), was characterized by X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The molecule was studied as a noninteracting system in the gas phase and in the solid state within a H-bonded network. With the support of DFT simulations of the spectra, it was found that the H-bonds mainly affect the N 1s level of the amino group, leaving the N 1s level of the pyridine-like N mostly unperturbed. This is responsible for a reduction of the chemical shift between the two XPS N 1s levels relative to free melamine. Consequently, N K-edge NEXAFS resonances involving the amino N 1s level also shift to lower photon energies. Moreover, the solid-state absorption spectra showed significant modification/quenching of resonances related to transitions from the amino N 1s level to σ* orbitals involving the NH2 termini. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimFile | Dimensione | Formato | |
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