Stevens, JS, Newton, LK, Jaye, C et al. (3 more authors) (2015) Proton Transfer, Hydrogen Bonding, and Disorder: Nitrogen Near-Edge X-ray Absorption Fine Structure and X-ray Photoelectron Spectroscopy of Bipyridine-Acid Salts and Co-crystals. Crystal Growth and Design, 15 (4). 1776 - 1783. ISSN 1528-7483
Abstract
The sensitivity of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to Brønsted donation and the protonation state of nitrogen in the solid state is investigated through a series of multicomponent bipyridine–acid systems alongside X-ray photoelectron spectroscopy (XPS) data. A large shift to high energy occurs for the 1s → 1π* resonance in the nitrogen K-edge NEXAFS with proton transfer from the acid to the bipyridine base molecule and allows assignment as a salt (C═NH+), with the peak ratio providing the stoichiometry of the types of nitrogen species present. A corresponding binding energy shift for C═NH+ is observed in the nitrogen XPS, clearly identifying protonation and formation of a salt. The similar magnitude shifts observed with both techniques relative to the unprotonated nitrogen of co-crystals (C═N) suggest that the chemical state (initial-state) effects dominate. Results from both techniques reveal the sensitivity to identify proton transfer, hydrogen bond disorder, and even the potential to distinguish variations in hydrogen bond length to nitrogen.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2015 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 10 Aug 2015 15:18 |
Last Modified: | 10 Aug 2015 15:18 |
Published Version: | http://dx.doi.org/10.1021/cg5018278 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/cg5018278 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:85724 |