Supramolecular covalency of halogen bond revealed by NMR contact shift in paramagnetic cocrystals

IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Anagha Sasikumar, Jan Novotny, Jan Chyba, Libor Kobera, Radek Marek
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引用次数: 0

Abstract

Despite the supramolecular interactions such as halogen bonding are frequently termed "noncovalent" interactions, they have been predicted using computational methods to possess a significant covalent component. In this article, we adopt a unique strategy that combines experimental solid-state NMR and relativistic DFT approaches to explore the electronic nature of previously postulated supramolecular covalency [Bora et al., Chem. Eur. J., 2017, 23, 7315]. Our approach involves analysis of hyperfine interactions and hyperfine shifts in NMR spectra of halogen-bonded cocrystals containing a paramagnetic transition-metal complex. We demonstrate that hyperfine interaction pertaining to the paramagnetic transition-metal center and being observed at the probed nucleus of the cocrystalized (halogen-bonded) molecule is governed by the Fermi-contact mechanism. This contact mechanism originates in "through-bond" spin transmission and, therefore, unequivocally reports on the electron sharing between the halogen-bonded molecules, i.e., halogen-bond covalency.
顺磁共晶中接触位移揭示的卤素键的超分子共价
尽管卤素键等超分子相互作用经常被称为“非共价”相互作用,但它们已经用计算方法预测具有重要的共价成分。在本文中,我们采用了一种独特的策略,结合了实验固态核磁共振和相对论DFT方法来探索先前假设的超分子共价的电子性质[Bora等人,化学]。欧元。[J].中国机械工程,2017,23(3):715。我们的方法包括分析含有顺磁性过渡金属配合物的卤素键合共晶的超精细相互作用和核磁共振光谱中的超精细位移。我们证明了在共晶(卤素键)分子的探测核上观察到的顺磁性过渡金属中心的超精细相互作用是由费米接触机制控制的。这种接触机制起源于“通键”自旋传输,因此,明确地报告了卤素键分子之间的电子共享,即卤素键共价。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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