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

Autor: Li G; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Stefanczyk O; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Kumar K; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Guerin L; Institute of Physics Rennes: Institut de physique de Rennes, Institut de Physique de Rennes, 35042, Rennes, FRANCE., Okuzono K; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Tran K; Leibniz Universität Hannover: Leibniz Universitat Hannover, Institute of Inorganic Chemistry, Callinstraße 9, 30167, Hannover, GERMANY., Kilic MS; Universität Hannover: Leibniz Universitat Hannover, Institute of Inorganic Chemistry, Callinstraße 9, 30167, Hannover, GERMANY., Nakabayashi K; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Imoto K; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Namai A; The University of Tokyo: Tokyo Daigaku, Department of Chemistry, School of Science, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN., Nakamura Y; Japan Synchrotron Radiation Research Institute: Koeki Zaidan Hojin Kokido Hikari Kagaku Kenkyu Center, SPring-8, 1-1-1, Kouto, Sayo-cho, 679-5198, Sayo, JAPAN., Maity SR; Japan Synchrotron Radiation Research Institute: Koeki Zaidan Hojin Kokido Hikari Kagaku Kenkyu Center, SPring-8, 1-1-1, Kouto, Sayo-cho, 679-5198, Sayo, JAPAN., Renz F; Universität Hannover: Leibniz Universitat Hannover, Institute of Inorganic Chemistry, Callinstraße 9, 30167, Hannover, GERMANY., Chastanet G; CNRS: Centre National de la Recherche Scientifique, Institute of Condensed Matter Chemistry of Bordeaux, 87 av. Dr A. Schweitzer, F-33600, Pessac, FRANCE., Ohkoshi SI; The University of Tokyo, Department of Chemistry, School of Science, 7-3-1, Hongo, Bunkyo-ku, 113-0033, Tokyo, JAPAN.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 11, pp. e202423095. Date of Electronic Publication: 2024 Dec 11.
DOI: 10.1002/anie.202423095
Abstrakt: 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.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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