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Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum

Naumova, Maria A. ; Kalinko, Aleksandr ; Wong, Joanne W.L. ; Alvarez Gutierrez, Sol ; Meng, Jie ; Liang, Mingli ; Abdellah, Mohamed LU ; Geng, Huifang LU ; Lin, Weihua LU and Kubicek, Katharina , et al. (2020) In The Journal of chemical physics 152(21).
Abstract

Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is... (More)

Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of chemical physics
volume
152
issue
21
article number
214301
publisher
American Institute of Physics (AIP)
external identifiers
  • scopus:85086354284
  • pmid:32505143
ISSN
0021-9606
DOI
10.1063/1.5138641
language
English
LU publication?
yes
id
2b39edb9-ca55-45ba-b493-51ab3509fd6c
date added to LUP
2020-07-03 09:30:52
date last changed
2024-05-01 12:50:05
@article{2b39edb9-ca55-45ba-b493-51ab3509fd6c,
  abstract     = {{<p>Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.</p>}},
  author       = {{Naumova, Maria A. and Kalinko, Aleksandr and Wong, Joanne W.L. and Alvarez Gutierrez, Sol and Meng, Jie and Liang, Mingli and Abdellah, Mohamed and Geng, Huifang and Lin, Weihua and Kubicek, Katharina and Biednov, Mykola and Lima, Frederico and Galler, Andreas and Zalden, Peter and Checchia, Stefano and Mante, Pierre Adrien and Zimara, Jennifer and Schwarzer, Dirk and Demeshko, Serhiy and Murzin, Vadim and Gosztola, David and Jarenmark, Martin and Zhang, Jianxin and Bauer, Matthias and Lawson Daku, Max Latevi and Khakhulin, Dmitry and Gawelda, Wojciech and Bressler, Christian and Meyer, Franc and Zheng, Kaibo and Canton, Sophie E.}},
  issn         = {{0021-9606}},
  language     = {{eng}},
  number       = {{21}},
  publisher    = {{American Institute of Physics (AIP)}},
  series       = {{The Journal of chemical physics}},
  title        = {{Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum}},
  url          = {{http://dx.doi.org/10.1063/1.5138641}},
  doi          = {{10.1063/1.5138641}},
  volume       = {{152}},
  year         = {{2020}},
}