Characterizing the Solvated Structure of Photoexcited [Os(terpy)2]2+ with X-ray Transient Absorption Spectroscopy and DFT Calculations

Xiaoyi Zhang; Mátyás Imre Pápai; Klaus Braagaard Møller; Jianxin Zhang; Sophie E. Canton

doi:10.3390/molecules21020235

Characterizing the Solvated Structure of Photoexcited [Os(terpy)₂]²⁺ with X-ray Transient Absorption Spectroscopy and DFT Calculations

Xiaoyi Zhang, Mátyás Imre Pápai, Klaus Braagaard Møller, Jianxin Zhang, Sophie E. Canton

Department of Chemistry

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

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 [OsN₆]. 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.

Original language	English
Journal	Molecules
Volume	21
Issue number	2
Number of pages	9
ISSN	1420-3049
DOIs	https://doi.org/10.3390/molecules21020235
Publication status	Published - 2016

Bibliographical note

This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Keywords

X-ray transient absorption spectroscopy
Excited-state
Osmium polypyridyl complex

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Characterizing the Solvated Structure of PhotoexcitedFinal published version, 2.12 MB

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COFUNDPostdocDTU: COFUNDPostdocDTU
Præstrud, M. R. (Project Participant) & Brodersen, S. W. (Project Participant)
01/01/2014 → 31/12/2019
Project: Research

Cite this

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title = "Characterizing the Solvated Structure of Photoexcited [Os(terpy)2]2+ with X-ray Transient Absorption Spectroscopy and DFT Calculations",

abstract = "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 [OsN6]. 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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AU - Pápai, Mátyás Imre

AU - Møller, Klaus Braagaard

AU - Zhang, Jianxin

AU - Canton, Sophie E.

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N2 - 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 [OsN6]. 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.

AB - 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 [OsN6]. 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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Characterizing the Solvated Structure of Photoexcited [Os(terpy)2]2+ with X-ray Transient Absorption Spectroscopy and DFT Calculations