The near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron (XP) spectra of gas-phase 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene (PPT) and triphenylphosphine oxide (TPPO) have been measured at the S and P LII,III-edge regions. The time-dependent density functional theory (TDDFT) based on the relativistic two-component zeroth-order regular approximation approach has been used to provide an assignment of the experimental spectra, giving the contribution of the spin-orbit splitting and of the molecular-field splitting to the sulfur and phosphor binding energies. Computed XP and NEXAFS spectra agree well with the experimental measurements. In going from dibenzothiophene and TPPO to PPT, the nature of the most intense S 2p and P 2p NEXAFS features are preserved; this trend suggests that the electronic and geometric behaviors of the S and P atoms in the two building block moieties are conserved in the more complex system of PPT. This work enables us to shed some light onto the structure of the P-O bond, a still highly debated topic in the chemical literature. Since the S 2p and P 2p NEXAFS intensities provide specific information on the higher-lying localized σ*(C-S) and σ*(P-O) virtual MOs, we have concluded that P 3d AOs are not involved in the formation of the P-O bond. Moreover, the results support the mechanism of negative hyperconjugation, by showing that transitions toward σ*(P-O) states occur at lower energies with respect to those toward π*(P-O) states.

S 2p and P 2p Core Level Spectroscopy of PPT Ambipolar Material and Its Building Block Moieties

Bernes E.;Fronzoni G.;Stener M.;Grazioli C.;De Simone M.;Toffoli D.
2020

Abstract

The near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron (XP) spectra of gas-phase 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene (PPT) and triphenylphosphine oxide (TPPO) have been measured at the S and P LII,III-edge regions. The time-dependent density functional theory (TDDFT) based on the relativistic two-component zeroth-order regular approximation approach has been used to provide an assignment of the experimental spectra, giving the contribution of the spin-orbit splitting and of the molecular-field splitting to the sulfur and phosphor binding energies. Computed XP and NEXAFS spectra agree well with the experimental measurements. In going from dibenzothiophene and TPPO to PPT, the nature of the most intense S 2p and P 2p NEXAFS features are preserved; this trend suggests that the electronic and geometric behaviors of the S and P atoms in the two building block moieties are conserved in the more complex system of PPT. This work enables us to shed some light onto the structure of the P-O bond, a still highly debated topic in the chemical literature. Since the S 2p and P 2p NEXAFS intensities provide specific information on the higher-lying localized σ*(C-S) and σ*(P-O) virtual MOs, we have concluded that P 3d AOs are not involved in the formation of the P-O bond. Moreover, the results support the mechanism of negative hyperconjugation, by showing that transitions toward σ*(P-O) states occur at lower energies with respect to those toward π*(P-O) states.
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https://pubs.acs.org/doi/10.1021/acs.jpcc.0c03973
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11368/2971446
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