Two Blatter Radicals Face-to-Face: A Constrained Diradical Architecture

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-12-20 DOI:10.1021/jacs.4c16500
Paulina Bartos, Dominika Pomikło, Kadin B. Sorenson, Oleksandr Hietsoi, Andrienne C. Friedli, Piotr Kaszyński
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Abstract

Cofacial arrangement of two Blatter radicals enforced by the peri-naphthalene scaffold represents a new approach to stable diradicals with strong through-space interactions. Two stereoisomers of the naphthalene-diradicals, anti and syn, are investigated by XRD, VT-EPR, UV–vis, electrochemical, kinetic, and DFT methods. In solutions, both stereoisomers exist as open-shell singlets with ΔES-T = −3.1 and −3.8 kcal mol–1, respectively. The anti isomer was resolved into enantiomers and converts to syn with ΔG298 = 23.6(8) kcal mol–1.

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两个布拉特激进分子面对面:一个受约束的双激进建筑
由周围萘支架强制的两个布拉特自由基的共面排列代表了一种具有强空间相互作用的稳定双自由基的新方法。采用XRD、VT-EPR、UV-vis、电化学、动力学和DFT等方法对萘二自由基的两种立体异构体进行了研究。在溶液中,这两种立体异构体都以开壳单重态存在,分别为ΔES-T =−3.1和−3.8 kcal mol-1。反异构体被分解为对映体并转化为syn, ΔG‡298 = 23.6(8)kcal mol-1。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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