Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety

Li，Wan Lu1; Zhang，Qingnan2; Chen，Mohua2; Hu，Han Shi1; Li，Jun1,3; Zhou，Mingfei2

2020

10.1002/anie.202000910

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Through reaction of beryllium dimers with carbon monoxide, a carbonyl complex BeBeCO is formed in solid neon. Upon visible light excitation, the BeBeCO complex rearranges to a BeCOBe isomer, which further isomerizes to a low-energy BeOBeC species under UV-visible light excitation. These species are identified on the basis of infrared absorption spectroscopy with isotopic substitutions and quantum chemical studies. The BeOBeC molecule is characterized to be a multiple radical species having an electronic quintet ground state featuring an unusual quartet carbyne unit with three unpaired electrons on the carbon center. Bonding analysis indicates that the strong Pauli repulsion between carbon 2s lone pair electrons and the σ electrons of the BeOBe fragment significantly weakens the Be−C bonding and destabilizes the triplet state of the BeOBeC radical with a doublet carbyne unit. The three-center π-bonding of BeOBe is also found to play a role in stabilizing the quartet carbyne.

beryllium matrix-isolation infrared spectroscopy multiple radicals quantum-chemical calculations quartet carbynes

SCI ; EI

英语

NI期刊

通讯

National Natural Science Foundation of China[21688102] ; National Natural Science Foundation of China[21590792] ; National Natural Science Foundation of China[91645203]

Chemistry

Chemistry, Multidisciplinary

WOS:000525279800043

WILEY-V C H VERLAG GMBH

20201208306968

Infrared spectroscopy ; Dimers ; Light ; Quantum chemistry ; Absorption spectroscopy ; Bond strength (chemical) ; Sulfur compounds ; Carbon monoxide ; Light absorption

Light/Optics:741.1 ; Physical Chemistry:801.4 ; Inorganic Compounds:804.2 ; Organic Polymers:815.1.1

CHEMISTRY

2-s2.0-85081563536

Scopus

1.Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education,Tsinghua University,Beijing,100084,China
2.Department of Chemistry,Collaborative Innovation Center of Chemistry for Energy Materials,Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials,Fudan University,Shanghai,200433,China
3.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Li，Wan Lu,Zhang，Qingnan,Chen，Mohua,et al. Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2020,59:6923-6928.

Li，Wan Lu,Zhang，Qingnan,Chen，Mohua,Hu，Han Shi,Li，Jun,&Zhou，Mingfei.(2020).Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,59,6923-6928.

Li，Wan Lu,et al."Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59(2020):6923-6928.