The application of gas phase and solid state X-ray photoelectron spectroscopy to the investigation of derivatives containing the repeating SN unit

Abstract

Solid state X-ray photoelectron spectra of S 2N 2, S 4N 4, (SNBr 0.04) x , and (SNBr 0.25) x have been obtained and the gas phase spectrum of S 2N 2 is also reported. Both the solid state and gas phase core level spectra, as well as MNDO and CHELEQ calculations, show that there is greater S → N charge transfer in S 4N 4 than in S 2N 2. The solid state data indicate that the charge distributions in S 2N 2 and (SN) x are the same. All of the data can be satisfactorily explained without recourse to N p π → S d π bonding. Bromination of an (SN) x film and single crystals results in complicated, broad N 1s and S 2p envelopes. Changes in the relative core level intensities on bromination suggest that the bromine resides largely between and/or on the (SN) x fibrils, rather than penetrating into the fibrils.