2024-05-28 パシフィック・ノースウェスト国立研究所(PNNL)
＜関連情報＞
- https://www.pnnl.gov/publications/organic-molecule-mimics-behavior-alkali-metals-electron-transfer-reactions
- https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202400038
有機分子がアルカリ金属を模倣し、ハロゲンとの自発的なハープーン反応を可能にする Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens
Dr. Wenjin Cao, Dr. Xue-Bin Wang
Chemistry – A European Journal Published: 29 January 2024
DOI:https://doi.org/10.1002/chem.202400038
Graphical Abstract
Octamethylcalix[4]pyrrole (omC4P) behaves like alkali metals and reacts with halogens (X) via the harpoon mechanism to form charge-separated omC4P+ ⋅ X− complexes.harpoon reactionlong range electron transferphotoelectron spectroscopy
Abstract
The harpoon mechanism has been a milestone in molecular reaction dynamics. Until now, the entity from which electron harpooning occurs has been either alkali metal atoms or non-metallic analogs in their excited states. In this work, we demonstrate that a common organic molecule, octamethylcalix[4] pyrrole (omC4P), behaves just like alkali metal atoms, enabling the formation of charge-separated ionic bonding complexes with halogens omC4P+ ⋅ X− (X=F−I, SCN) via the harpoon mechanism. Their electronic structures and chemical bonding were determined by cryogenic photoelectron spectroscopy of the corresponding anions and confirmed by theoretical analyses. The omC4P+ ⋅ X− could be visualized to form from the reactants omC4P+X via electron harpooning from omC4P to X at a distance defined by the energy difference between the ionization potential of omC4P and electron affinity of X.
