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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...

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Autores principales: Zhang, Xiaoyi, Pápai, Mátyás, Møller, Klaus B., Zhang, Jianxin, Canton, Sophie E.
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
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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.
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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
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