可光切换的阿佐比斯皮拉晶体实现近量化晶体状态双向E Z转换
Yixin He1,2, Tongtong Dang1, Andrew G Leach2
1School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai 200240, China.
Journal of the American Chemical Society
|October 14, 2024
概括
这项研究引入了亚比斯皮拉晶体,这是第一个能在固态状态下实现高双向EZ异构的可光切换亚晶体. 由于其独特的晶体光交换能力,这些光敏材料具有先进应用的潜力.
科学领域:
- 材料科学
- 有机化学
- 晶体学
背景情况:
- 亚分子是众所周知的光开关,在溶液中表现出色,但由于分子包装而面临固态异构化的挑战.
- 在晶化合物中实现高效的EZ异构是困难的,因为构成自由度有限.
研究的目的:
- 为了研究亚比斯皮拉分子的固态光交换性能.
- 在晶体亚比斯皮拉中展示高产量的双向EZ异构.
- 为了阐明高效晶体光交换背后的机制.
主要方法:
- 合成和表征阿佐比斯皮拉化合物
- 固态光化学研究以确定EZ转换效率.
- 晶体分析以了解分子包装和相互作用.
- 计算机建模以探索光交换机制.
主要成果:
- 阿佐比斯皮拉晶体具有较高的E→Z光转换 (85%96%) 和定量Z→E光交换.
- 这些是首次报告的具有高产量的双向转换的可光交换晶,包括具有挑战性的E→Z转换.
- 晶体学和计算数据表明,晶体自由空间和弱分子间相互作用促进异构.
结论:
- 在固态化学中,阿佐比斯皮拉是突破性的,使其能够在晶体形式中实现高效的双向光交换.
- 这些发现突出了晶体结构的关键作用,包括自由空间和分子间力量,使固态异构成为可能.
- 这项研究为设计响应光的晶及其应用开辟了新的可能性.
相关概念视频
01:34The Z-Scheme of Electron Transport in Photosynthesis
The light reactions of photosynthesis assume a linear flow of electrons from water to NADP+. During this process, light energy drives the splitting of water molecules to produce oxygen. However, oxidation of water molecules is a thermodynamically unfavorable reaction and requires a strong oxidizing agent. This is accomplished by the first product of light reactions: oxidized P680 (or P680+), the most powerful oxidizing agent known in biology. The oxidized P680 that acquires an electron from the...
01:26Photochemical Electrocyclic Reactions: Stereochemistry
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
01:27Symmetry Elements in a Crystal
Crystal symmetry operations are isometric transformations that map objects onto indistinguishable copies while preserving distances, angles, and volumes. The simplest symmetry operation is translation, which shifts the entire infinite crystal lattice parallelly by a translation vector.Crystallographic rotations involve rotations by an angle of 2π/n around an axis without changing the positions of points on the axis. It is called the rotational axis of the symmetry, denoted by n. The combination...
01:29Determination of Crystal Structures
In the late 1800s, the revelation that light extended beyond visible wavelengths led to the discovery of X-rays by Wilhelm Roentgen. Recognized as high-energy electromagnetic radiation with short wavelengths, X-rays prompted exploration into their interaction with crystals. Max von Laue proposed in 1912 that the periodic arrangement of atoms, ions, or molecules in crystals would cause them to diffract X-rays, a hypothesis confirmed through experiments with copper sulfate and zinc sulfide...