インターバレンスの電荷移転を表示する分散型混合バレンスの二核イテルビウム複合体
Tom J N Obey1, Mukesh K Singh1, Angelos B Canaj1
1EaStCHEM School of Chemistry, University of Edinburgh, EH9 3FJ, Edinburgh, United Kingdom.
Journal of the American Chemical Society
|October 14, 2024
まとめ
研究者は異地化酸化状態を示す稀な混合バレンスのイテルビウム複合体を合成した. この研究は,f-fトランジションによるロビン・デイクラスIII複合体における間隔電荷移転 (IVCT) の最初の観測を報告している.
科学分野:
- 無機化学
- 材料科学
- 写真化学
背景:
- 混合ヴァレンスの化合物における間隔電荷移転 (IVCT) 分析は,分子電子と人工光合成における電子移転を理解するために重要である.
- ランタニド混合バレンスの複合体は合成が難しいが,局所的バレンスのIVCT現象またはd-d金属結合を示す.
- 既存の研究は主にロビン・デイ・クラスII複合体に焦点を当てており,クラスIIIシステムの理解は限られている.
研究 の 目的:
- 稀なロビン・デイ III級複合体の合成と特徴付け
- このユニークなイタービウム複合体の 電子構造と伝送特性を調べるためだ
- クラスIIIのシステムにおけるf-fトランジションから生じる間隔電荷移転 (IVCT) を観察し,分析する.
主な方法:
- 単体二核イテルビウム複合体の合成
- 顕微鏡と電気化学技術を用いた特徴付け.
- 酸化状態と電子構造を決定する計算分析.
主要な成果:
- 稀なロビン・デイ・クラスIIIの単体二核イテルビウム複合体の合成と特徴付けに成功した.
- 複合体は,クラスIIのシステムにおける局所的バレンシーとは異なる非局所的酸化状態を示す.
- ロビン・デイ・クラスIII複合体におけるIVCTの最初の観測は,金属対金属結合のないf-f電子トランジションに起因する.
結論:
- この研究は,異地化されたイテルビウム酸化状態を有するロビン・デイ・クラスIII混合バレンスの複合体の希少な例を示している.
- 観測されたIVCT現象はf-fトランジションによって駆動され,ランタナイド系における電子移転機構の理解を広げている.
- この発見は,分子電子とエネルギー変換の応用のための機能的な材料の設計に新しい道を開きます.
さらに関連する動画
16:11Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
2.2K
08:54Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
Published on: January 25, 2020
5.6K
関連する概念動画
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.7K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
41.7K
02:42Valence Bond Theory
8.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.5K
02:58Crystal Field Theory - Octahedral Complexes
26.2K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.2K
01:19Complexation Equilibria: The Chelate Effect
470
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
470
01:22EDTA: Chemistry and Properties
1.8K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
1.8K
03:02Colors and Magnetism
11.6K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.6K