Cargando…
Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations
Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of “red sensitizers” based on osmium(II) polypyridyl compounds often undergoe...
Autores principales: | , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2016
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6273819/ https://www.ncbi.nlm.nih.gov/pubmed/26907233 http://dx.doi.org/10.3390/molecules21020235 |
_version_ | 1783377475496050688 |
---|---|
author | Zhang, Xiaoyi Pápai, Mátyás Møller, Klaus B. Zhang, Jianxin Canton, Sophie E. |
author_facet | Zhang, Xiaoyi Pápai, Mátyás Møller, Klaus B. Zhang, Jianxin Canton, Sophie E. |
author_sort | Zhang, Xiaoyi |
collection | PubMed |
description | Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of “red sensitizers” based on osmium(II) polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy)(2)](2+) (terpy: 2,2′:6′,2″-terpyridine) solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN(6)]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT) and the near-edge region of the X-ray spectra. |
format | Online Article Text |
id | pubmed-6273819 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-62738192018-12-28 Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations Zhang, Xiaoyi Pápai, Mátyás Møller, Klaus B. Zhang, Jianxin Canton, Sophie E. Molecules Article Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of “red sensitizers” based on osmium(II) polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy)(2)](2+) (terpy: 2,2′:6′,2″-terpyridine) solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN(6)]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT) and the near-edge region of the X-ray spectra. MDPI 2016-02-19 /pmc/articles/PMC6273819/ /pubmed/26907233 http://dx.doi.org/10.3390/molecules21020235 Text en © 2016 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons by Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Zhang, Xiaoyi Pápai, Mátyás Møller, Klaus B. Zhang, Jianxin Canton, Sophie E. Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title | Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title_full | Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title_fullStr | Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title_full_unstemmed | Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title_short | Characterizing the Solvated Structure of Photoexcited [Os(terpy)(2)](2+) with X-ray Transient Absorption Spectroscopy and DFT Calculations |
title_sort | characterizing the solvated structure of photoexcited [os(terpy)(2)](2+) with x-ray transient absorption spectroscopy and dft calculations |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6273819/ https://www.ncbi.nlm.nih.gov/pubmed/26907233 http://dx.doi.org/10.3390/molecules21020235 |
work_keys_str_mv | AT zhangxiaoyi characterizingthesolvatedstructureofphotoexcitedosterpy22withxraytransientabsorptionspectroscopyanddftcalculations AT papaimatyas characterizingthesolvatedstructureofphotoexcitedosterpy22withxraytransientabsorptionspectroscopyanddftcalculations AT møllerklausb characterizingthesolvatedstructureofphotoexcitedosterpy22withxraytransientabsorptionspectroscopyanddftcalculations AT zhangjianxin characterizingthesolvatedstructureofphotoexcitedosterpy22withxraytransientabsorptionspectroscopyanddftcalculations AT cantonsophiee characterizingthesolvatedstructureofphotoexcitedosterpy22withxraytransientabsorptionspectroscopyanddftcalculations |