Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens

Cao, Wenjin; Wang, Xue‐Bin

doi:10.1002/chem.202400038

Title: Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens

Journal Article · Fri Feb 16 00:00:00 UTC 2024 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202400038 · OSTI ID:2308889

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Physical Sciences Division Pacific Northwest National Laboratory 902 Battelle Boulevard, P. O. Box 999, MS J7-10 Richland WA 99352 USA

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 .

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2308889

Report Number(s):: PNNL-SA--193929; e202400038

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 20 Vol. 30; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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