Activating weak electrophiles to break nonpolar C-C bonds with electric fields

Activating weak electrophiles to break nonpolar C-C bonds with electric fields

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Xueyan Zhao^a, Adila Adijiang^a, Dong Xiang^a^,^b^,^*

Chinese Chemical Letters | 2023, 34(11) : 108381

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Chinese Chemical Letters | 2023, 34(11): 108381

• Editorial •

Activating weak electrophiles to break nonpolar C-C bonds with electric fields

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Xueyan Zhao^a, Adila Adijiang^a, Dong Xiang^a^,^b^,^*

Affiliations

^a Institute of Modern Optics and Center of Single-Molecule Science,Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology,Nankai University,Tianjin 300350,China

^b School of Materials Science and Engineering,Smart Sensing Interdisciplinary Science Center,Nankai University,Tianjin 300350,China

Published: 2023-11-15 doi: 10.1016/j.cclet.2023.108381

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Xueyan Zhao, Adila Adijiang, Dong Xiang. Activating weak electrophiles to break nonpolar C-C bonds with electric fields[J]. Chinese Chemical Letters, 2023 , 34 (11) : 108381 - . DOI: 10.1016/j.cclet.2023.108381

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Electrophilic aromatic substitution (EAS) is a vital chemical reaction in organic chemistry that involves replacing substituent on an aromatic ring by an electrophile. Despite its widespread industrial applications in the production of substituted aromatic compounds,the reaction typically requires harsh reaction conditions,such as high temperature and potent Lewis acid catalysts,to activate the electrophile due to the stability of the aromatic ring [1].

Recently,a study published by Yaping Zang and colleagues in Nature Communications demonstrates the use of an electric field as a catalyst to regulate EAS reactivity,replacing conventional chemical reagents. The research team discovered that an electric field could activate an otherwise unreactive electrophile and break inert nonpolar C-C bonds under mild conditions. These unprecedented results showcase the potential for broadening the scope of EAS reactions via electric field catalysis.

Previous research has explored various chemical reactions catalyzed by oriented external electric field (OEEF) [2-4]. While OEEF can theoretically promote charge separation and catalyze EAS reactions,achieving the necessary large electric field using traditional ensemble techniques has proven difficult [5,6]. Additionally,OEEF has strict requirements for orientation,with an almost perpendicular alignment needed to promote electrophilic attack and charge transfer [7]. Achieving this microscopic alignment is highly challenging in experiments.

To overcome these challenges,the team employed the scanning tunneling microscopy break junction (STM-BJ) technique to investigate the OEEF-catalyzed EAS reaction of a range of hoop-shaped hydrocarbons (Fig. 1) [8]. The STM-BJ method enables the creation of a sufficiently large OEEF within an Au tip-substrate nanogap upon a bias voltage. Furthermore,the molecules' distinct radial π-conjugated structure enables the OEEF perpendicular to the aromatic ring,achieving optimal alignment of the OEEF along the EAS reaction axis.

Based on this technique,the team demonstrate that the OEEF can significantly accelerate the EAS by the otherwise unreactive Au electrophile under very mild conditions (using a bias voltage of < 1 V). This EAS reaction cleaves the inherently inert C(sp²)-C(sp²) bond,which is of great importance in synthetic chemistry but generally very difficult to realize. These OEEF-catalyzed EAS reactions result in a ~97% high-yield production of linear oligophenylenes terminated with covalent Au-C bonds. Density functional theory (DFT)-based calculations reveal a classic two-step mechanism in the EAS reactions,in which the electric field plays a critical role in promoting the formation of the key charge-separated σ-complex intermediate.

This work represents a significant advancement in the application of single-molecule techniques to electric field catalysis of chemical reactions. Through a series of well-designed experiments,it provides compelling evidence that OEEF can serve as a catalyst for EAS reactions. This research also opens up new avenues for investigating the mechanisms underlying classical organic reactions and demonstrates the potential of single-molecule technology to realize challenging chemical reactions.

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Year 2023 volume 34 Issue 11

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doi: 10.1016/j.cclet.2023.108381

Online Date：2025-11-21
Published：2023-11-15

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Affiliations

^a Institute of Modern Optics and Center of Single-Molecule Science,Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology,Nankai University,Tianjin 300350,China

^b School of Materials Science and Engineering,Smart Sensing Interdisciplinary Science Center,Nankai University,Tianjin 300350,China

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表12种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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