阿希拉尔Au (I) 循环三核复合体,具有高效循环极化近红外TADF
Hu Yang1, Su-Kao Peng1, Ji Zheng1
1College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou, Guangdong 510632, P. R. China.
Angewandte Chemie (International ed. in English)
|August 28, 2023
概括
两个新的黄金I) 复合物Cl-Au和Br-Au在近红外 (NIR) 区域实现了高光发光量子产量 (PLQY),为先进的发光材料提供了高效的热激活延迟光 (TADF).
科学领域:
- 材料科学 材料科学 材料科学
- 摄影化学的使用.
- 超分子化学 超分子化学
背景情况:
- 在近红外 (NIR) 区域实现高光发光量子收益率 (PLQY) 对发光材料至关重要,特别是在热激活延迟光 (TADF) 应用中.
- 现有的NIR-TADF发射器在实现高效率和固态性能方面经常面临挑战.
研究的目的:
- 为NIR-TADF应用合成和表征新型Achiral循环三核黄金 (I) 复合物.
- 研究这些新型黄金复合物的光物理性质,包括PLQY和循环极化发光 (CPL).
- 探索这些材料在应用中的潜力,例如具有防伪功能的3D打印发光标志.
主要方法:
- 合成两个阿希拉尔循环三核黄金 (((I) 复合物,Au3 (((4-Clpyrazolate) 3 (Cl-Au) 和Au3 (((4-Brpyrazolate) 3 (Br-Au),通过pyrazole衍生物与Au (((I) 盐的反应.
- 光物理特征包括PLQY测量,吸收和辐射光谱以及时间分辨率发光研究.
- 理论计算 (例如,DFT) 来理解TADF属性的电子结构和起源.
- 结晶学分析以确定晶体结构和空间组.
- 循环极化发光 (CPL) 光谱法用于评估手术特征.
- 使用Cl-Au作为发射墨水制造3D打印的发光标志.
主要成果:
- Cl-Au 和 Br-Au 复合体在 NIR I 区域 (λmax = 720 nm) 均表现出高效的 NIR-TADF,PLQY 高 (>70%),性能优于现有的固态 NIR-TADF 发射器.
- 高效的TADF属性归因于一个小的能量差距 (ΔE(S1-T2) 和大型的自旋轨道合,由分子聚合物中的合物-金属-金属电荷转移驱动.
- 这两种复合体都在阿基拉Pna21空间组中结晶,并显示具有显著发光不对称系数 (Racingg_lum Handus) 的CPL活动.
- 用Cl-Au制造的3D打印发光标志展示了由于其CPL行为而具有防伪能力,这取决于结晶性.
结论:
- 开发的Achiral循环三核黄金 (I) 复合体是非常有前途的NIR-TADF发射器,具有出色的固态性能.
- 该研究强调了连接体设计和超分子聚合在实现高效的NIR-TADF和CPL特性方面的潜力.
- 成功制造CPL活跃的3D打印标志展示了这些材料在防伪技术中的实际应用.
相关概念视频
01:18Aromatic Hydrocarbon Cations: Structural Overview
2.8K
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...
Removing one hydrogen from the intervening CH2 group...
2.8K
01:42The Antenna Complex
6.0K
Plants and other photosynthetic organisms comprise pigments capable of absorption of direct sunlight. These pigments are present in the reaction center - the main site of photochemical reactions as well as in the antenna complex. Under average light conditions, the rate at which reaction center pigments absorb light is far below the electron transport chain's capacity. As a result, the reaction center alone cannot provide enough energy to drive photosynthesis. The photosynthetic efficiency...
6.0K
02:58Crystal Field Theory - Octahedral Complexes
26.7K
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...
26.7K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
42.9K
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,...
42.9K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
1.9K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.9K
03:02Colors and Magnetism
11.8K
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...
11.8K