具有190ns金属至配体电荷转移寿命的 (I) 复合物
Sandra Kronenberger1, Robert Naumann1, Christoph Förster1
1Department of Chemistry, Johannes Gutenberg University Mainz, Mainz, Germany.
Nature communications
|August 22, 2025
概括
这项研究引入了具有长寿命激发状态的复合物,使可持续的光化学成为可能. 这种丰富的金属复合物在光活性方面与贵金属相美,
科学领域:
- 无机化学
- 摄影化学
- 材料科学
背景情况:
- 光活性过渡金属复合物通常依赖于具有长寿命三重金属到连接体 (3MLCT) 电荷转移状态 (>100 ns) 的贵金属 (4/5d6配置).
- 丰富的3d6金属复合物通常具有短的兴奋状态寿命 (<2 ns) 和复杂的合成,阻碍了实际使用.
研究的目的:
- 开发光活性3d6金属复合物,使用与贵金属复合物相比的丰富的金属.
- 探索复合物与刚性碳/二烯配体在可持续光化学中的潜力.
主要方法:
- 从商业上可用的 bis (imidazolium) 基和 (II) 盐中合成一个四基 (Mn (pbmi)) +复合物.
- 复合物的光物理性质的表征,包括光寿命和氧化还原行为.
主要成果:
- 合成的[Mn(pbmi) 2+复合物从3MLCT状态呈现室温光,在液体溶液中使用寿命为190ns.
- 该复合物具有可逆的氧化还原过程 ([Mn(pbmi) 2+/+) 和能够减少的兴奋状态.
- 获得激发状态的寿命与贵重金属复合体相美, 证明了地球上大量替代品的潜力.
结论:
- 与刚性卡/皮里丁连接体的 (I) 复合体为产生具有长寿命3MLCT状态的光活性3d6金属复合体提供了可行的策略.
- 这项工作为开发利用土壤丰富的金属的可持续光化学应用提供了概念基础.
相关概念视频
02:51Metal-Ligand Bonds
21.5K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
21.5K
01:19Complexation Equilibria: The Chelate Effect
659
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...
659
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
471
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
471
03:45Formation of Complex Ions
24.0K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
24.0K
01:07Ladder Diagrams: Complexation Equilibria
421
Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
421
03:02Colors and Magnetism
12.3K
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...
12.3K