Near-Infrared Light-Induced Spin-State Switching Based on Fe(II)−Hg(II) Spin-Crossover Network

verfasst von: Guanping Li, Olaf Stefanczyk, Kunal Kumar, Laurent Guérin, Kosei Okuzono, Kevin Tran, Maximilian Seydi Kilic, Koji Nakabayashi, Kenta Imoto, Asuka Namai, Yuiga Nakamura, Sumit Ranjan Maity, Franz Renz, Guillaume Chastanet, Shin ichi Ohkoshi
Abstract: The development of molecular switches with tunable properties has garnered considerable interest over several decades. A novel spin-crossover (SCO) material based on iron(II) complexes incorporating 4-acetylpyridine (4-acpy) and [Hg(SCN)₄]²⁻ anions was synthesized and formulated as [Fe(4-acpy)₂][Hg(μ-SCN)₄] (1). Compound 1 is crystallized in a three-dimensional network in the non-centrosymmetric orthorhombic space group Pna2₁ with two octahedral [Fe(4-acpy)₂(NCS)₄] entities featuring two distinct Fe centers (Fe1 and Fe2). Crystallographic, magnetic, and Mössbauer measurements reveal an incomplete SCO exclusively at Fe2, with transition temperature T_1/2≈102 K. Photomagnetic studies conducted at 10 K with lasers ranging from 405 to 1310 nm evidence light-induced excited spin-state trapping (LIESST) and reverse-LIESST effects, with a unique near-infrared-responsive LIESST phenomenon at 1064 and 1310 nm. Advanced photocrystallographic studies at 40 K provide precise structural evidence for these metastable states. The optical and vibrational properties consistently corroborate with magnetic and photomagnetic studies. Additionally, temperature- and light-dependent terahertz (THz) absorptions are associated with phonon vibrations around Fe2 centers, through SCO behavior, as supported by ab initio calculation. The Fe(II)−Hg(II) systems can be promising benchmarks for exploring synergistic switching effects in structural, magnetic, and spectroscopic properties.
Organisationseinheit(en): Institut für Anorganische Chemie
Hannover School for Nanotechnology
Laboratorium für Nano- und Quantenengineering
Externe Organisation(en): University of Tokyo (UTokyo)
University of Manchester
Universite de Rennes 1
Japan Synchrotron Radiation Research Institute
Universite de Bordeaux
Typ: Artikel
Journal: Angewandte Chemie - International Edition
Anzahl der Seiten: 13
ISSN: 1433-7851
Publikationsdatum: 11.12.2024
Publikationsstatus: Elektronisch veröffentlicht (E-Pub)
Peer-reviewed: Ja
ASJC Scopus Sachgebiete: Katalyse, Allgemeine Chemie
Elektronische Version(en): https://doi.org/10.1002/anie.202423095 (Zugang: Offen)

BibTeX

@article{d80ccc12033043aa9a9faf71b32d1c7b,
title = "Near-Infrared Light-Induced Spin-State Switching Based on Fe(II)−Hg(II) Spin-Crossover Network",
abstract = "The development of molecular switches with tunable properties has garnered considerable interest over several decades. A novel spin-crossover (SCO) material based on iron(II) complexes incorporating 4-acetylpyridine (4-acpy) and [Hg(SCN)4]2− anions was synthesized and formulated as [Fe(4-acpy)2][Hg(μ-SCN)4] (1). Compound 1 is crystallized in a three-dimensional network in the non-centrosymmetric orthorhombic space group Pna21 with two octahedral [Fe(4-acpy)2(NCS)4] entities featuring two distinct Fe centers (Fe1 and Fe2). Crystallographic, magnetic, and M{\"o}ssbauer measurements reveal an incomplete SCO exclusively at Fe2, with transition temperature T1/2≈102 K. Photomagnetic studies conducted at 10 K with lasers ranging from 405 to 1310 nm evidence light-induced excited spin-state trapping (LIESST) and reverse-LIESST effects, with a unique near-infrared-responsive LIESST phenomenon at 1064 and 1310 nm. Advanced photocrystallographic studies at 40 K provide precise structural evidence for these metastable states. The optical and vibrational properties consistently corroborate with magnetic and photomagnetic studies. Additionally, temperature- and light-dependent terahertz (THz) absorptions are associated with phonon vibrations around Fe2 centers, through SCO behavior, as supported by ab initio calculation. The Fe(II)−Hg(II) systems can be promising benchmarks for exploring synergistic switching effects in structural, magnetic, and spectroscopic properties.",
keywords = "Ab Initio Calculations, Iron(II) Complexes, Photo-magnetism, Spin-crossover, Terahertz Spectroscopy",
author = "Guanping Li and Olaf Stefanczyk and Kunal Kumar and Laurent Gu{\'e}rin and Kosei Okuzono and Kevin Tran and {Seydi Kilic}, Maximilian and Koji Nakabayashi and Kenta Imoto and Asuka Namai and Yuiga Nakamura and {Ranjan Maity}, Sumit and Franz Renz and Guillaume Chastanet and Ohkoshi, {Shin ichi}",
note = "Publisher Copyright: {\textcopyright} 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.",
year = "2024",
month = dec,
day = "11",
doi = "10.1002/anie.202423095",
language = "English",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
}