Renewable bromide storage with antioxidant properties: Novel tribromide Br3- salt with bis(triphenylphosphine oxide)hydron

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-03-20 DOI:10.1016/j.molstruc.2025.142110

A.S. Berezin

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引用次数: 0

Abstract

The novel tribromide {Br₃}^1- salt, [{H(OPPh₃)₂}Br₃] (1), featuring the rarely observed bis(triphenylphosphine oxide)hydron cation was isolated via several methods. Compound 1 was found to transform to the initial triphenylphosphine oxide ([OPPh₃]∙½H₂O) through four intermediate stages. These intermediates, [{H₃O(OPPh₃)₃}Br₃] (2), [{H(OPPh₃)₂}{H₃O(OPPh₃)₂}{Br}{Br₃}] (3), and [H₃O(OPPh₃)₂Br] (4), were isolated by controlling crystallization conditions. This study reports the synthesis, crystal structures of four compounds 1–4, and photophysical properties of 1 both in solid state and ethanolic solution. Solid 1 exhibits the two low-energy absorption bands in the 4.5-1.8 eV energy range assigned to the transitions within the {Br₃}^1- moiety with weak exciton-phonon coupling. The third transition, attributed to transitions within the {H(OPPh₃)₂}¹⁺ cation, characterizes higher vibration energy and stronger exciton-phonon coupling. Compound 1 demonstrates antioxidant properties by neutralizing the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical following brominating to form mono- and di-brominated DPPH derivatives. The kinetics of DPPH bromination and subsequent neutralization was found to follow pseudo-first-order reaction behavior.

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.