{"title":"Understanding spin-dependent vibrational frequencies in Fe(II) metal organic coordination complexes","authors":"","doi":"10.1016/j.cap.2024.09.007","DOIUrl":null,"url":null,"abstract":"<div><p>We investigated the compositional and temperature (<em>T</em>) dependences of vibrational frequencies in Hofmann-type Fe(<em>L</em>)<sub>2</sub>[<em>M</em>(CN)<sub>4</sub>] spin-crossover (SCO) coordination polymers in which {<em>M</em> = Ni, Pd or Pt with <em>L</em> = pyridine (py)}, or {<em>L</em> = 3-Cl-py or 3-methylpy with <em>M</em> = Ni}, using Raman spectroscopy. The SCO-driven peak shifts (in wavenumber) ranged up to ∼170 cm<sup>−1</sup>, manifesting significant spin-dependent structural evolutions. Furthermore, there appear clear HS signatures even at <em>T</em> ≪ <em>T</em><sub>SCO</sub> for <em>L</em> = 3-Cl-py or 3-methylpy implying the steric effects of the organic ligands on the HS trapping. Meanwhile, for <em>L</em> = py, such HS trapping at the low temperature was not significant although some spectra taken under high laser fluence exhibit light-induced excited spin state trapping (LIESST) effect. The mechanism of the LIESST is discussed in detail in terms of the <em>M</em> d – C 2sp hybridization effects.</p></div>","PeriodicalId":11037,"journal":{"name":"Current Applied Physics","volume":null,"pages":null},"PeriodicalIF":2.4000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Current Applied Physics","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1567173924002074","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
我们利用拉曼光谱研究了霍夫曼型 Fe(L)2[M(CN)4] 自旋交叉（SCO）配位聚合物（其中 {M = Ni、Pd 或 Pt，L = 吡啶 (py)} 或 {L = 3-Cl-py 或 3-甲基py，M = Ni}）振动频率的组成和温度（T）依赖性。SCO 驱动的峰值偏移（以波长表示）范围高达 ∼170 cm-1，显示出显著的自旋依赖性结构演变。此外，对于 L = 3-Cl-py 或 3-methylpy 来说，即使在 T≪ TSCO 时也会出现明显的 HS 信号，这意味着有机配体对 HS 捕获的立体效应。同时，对于 L = py，虽然在高激光通量下拍摄的一些光谱显示了光诱导激发自旋态捕获（LIESST）效应，但这种低温下的 HS 捕获并不显著。本文从 M d - C 2sp 杂化效应的角度详细讨论了 LIESST 的机理。
Understanding spin-dependent vibrational frequencies in Fe(II) metal organic coordination complexes
We investigated the compositional and temperature (T) dependences of vibrational frequencies in Hofmann-type Fe(L)2[M(CN)4] spin-crossover (SCO) coordination polymers in which {M = Ni, Pd or Pt with L = pyridine (py)}, or {L = 3-Cl-py or 3-methylpy with M = Ni}, using Raman spectroscopy. The SCO-driven peak shifts (in wavenumber) ranged up to ∼170 cm−1, manifesting significant spin-dependent structural evolutions. Furthermore, there appear clear HS signatures even at T ≪ TSCO for L = 3-Cl-py or 3-methylpy implying the steric effects of the organic ligands on the HS trapping. Meanwhile, for L = py, such HS trapping at the low temperature was not significant although some spectra taken under high laser fluence exhibit light-induced excited spin state trapping (LIESST) effect. The mechanism of the LIESST is discussed in detail in terms of the M d – C 2sp hybridization effects.
期刊介绍：
Current Applied Physics (Curr. Appl. Phys.) is a monthly published international journal covering all the fields of applied science investigating the physics of the advanced materials for future applications.
Other areas covered: Experimental and theoretical aspects of advanced materials and devices dealing with synthesis or structural chemistry, physical and electronic properties, photonics, engineering applications, and uniquely pertinent measurement or analytical techniques.
Current Applied Physics, published since 2001, covers physics, chemistry and materials science, including bio-materials, with their engineering aspects. It is a truly interdisciplinary journal opening a forum for scientists of all related fields, a unique point of the journal discriminating it from other worldwide and/or Pacific Rim applied physics journals.
Regular research papers, letters and review articles with contents meeting the scope of the journal will be considered for publication after peer review.
The Journal is owned by the Korean Physical Society.
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