Details
| Original language | English |
|---|---|
| Number of pages | 13 |
| Journal | Angewandte Chemie - International Edition |
| Early online date | 11 Dec 2024 |
| Publication status | E-pub ahead of print - 11 Dec 2024 |
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 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
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
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In: Angewandte Chemie - International Edition, 11.12.2024.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Near-Infrared Light-Induced Spin-State Switching Based on Fe(II)−Hg(II) Spin-Crossover Network
AU - Li, Guanping
AU - Stefanczyk, Olaf
AU - Kumar, Kunal
AU - Guérin, Laurent
AU - Okuzono, Kosei
AU - Tran, Kevin
AU - Seydi Kilic, Maximilian
AU - Nakabayashi, Koji
AU - Imoto, Kenta
AU - Namai, Asuka
AU - Nakamura, Yuiga
AU - Ranjan Maity, Sumit
AU - Renz, Franz
AU - Chastanet, Guillaume
AU - Ohkoshi, Shin ichi
N1 - Publisher Copyright: © 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2024/12/11
Y1 - 2024/12/11
N2 - 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 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.
AB - 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 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.
KW - Ab Initio Calculations
KW - Iron(II) Complexes
KW - Photo-magnetism
KW - Spin-crossover
KW - Terahertz Spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85212503927&partnerID=8YFLogxK
U2 - 10.1002/anie.202423095
DO - 10.1002/anie.202423095
M3 - Article
AN - SCOPUS:85212503927
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
ER -