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Supplementary information files for Synthesis and characterization of Craig-type antiaromatic species with [4n + 2] π electrons

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posted on 2023-02-23, 16:33 authored by Lu Lin, Amit Ranjan Nath, Qin Zhu, Zhixin Chen, Jingjing Wu, Hongjian Wang, Qian Li, Wen-Feng LinWen-Feng Lin, Jun Zhu, Haiping Xia

Supplementary files for article Synthesis and characterization of Craig-type antiaromatic species with [4n + 2] π electrons


Antiaromaticity is extended from aromaticity as a complement to describe the unsaturated cyclic molecules with antiaromatic destabilization. To prepare antiaromatic species is a particularly challenging goal in synthetic chemistry because of the thermodynamic instability of such molecules. Among that, both Hückel and Möbius antiaromatic species have been reported, whereas the Craig one has not been realized to date. Here, we report the first example of planar Craig antiaromatic species. Eight Craig antiaromatic compounds were synthesized by deprotonation-induced reduction process and were fully characterized as follows. Single-crystal X-ray crystallography showed that these complexes have planar structures composed of fused five-membered rings with clearly alternating carbon–carbon bond lengths. In addition, proton NMR (1H NMR) spectroscopy in these structures showed distinctive upfield shifts of the proton peaks to the range of antiaromatic peripheral hydrogens. Experimental spectroscopy observations, along with density-functional theory (DFT) calculations, provided evidence for the Craig antiaromaticity of these complexes. Further study experimentally and theoretically revealed that the strong exothermicity of the acid-base neutralization process was the driving force for this challenging transformation forming Craig antiaromatic species. Our findings complete a full cycle of aromatic chemistry, opening an avenue for the development of new class of antiaromatic systems. 


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Engineering and Physical Sciences Research Council

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National Natural Science Foundation of China (Nos. 92156021, 21873079, and 21931002)

Shenzhen Science and Technology Innovation Committee (no. JCYJ20200109140812302)

Guangdong Provincial Key Laboratory of Catalysis (no. 2020B121201002)

Top-Notch Young Talents Program of China and the Financial Support for Outstanding Talents Training Fund in Shenzhen



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