A Room-Temperature Stable Distonic Radical Cation

Chen，Xiaodan1; Liu，Liu Leo2; Liu，Shihua3,4; Grützmacher，Hansjörg3,4,5; Li，Zhongshu3,4

2020

10.1002/ANGE.202011677

ADVANCED MATERIALS   Impact Factor & Quartile

0935-9648

1521-4095

Distonic radical cations (DRCs) with spatially separated charge and radical sites have, so far, largely been observed by gas-phase mass spectrometry and/or matrix isolation spectroscopy work. Herein, we disclose the isolation of a crystalline dicarbondiphosphide-based /3-distonic radical cati on sa It 3 (BARF) (BARF=[B(3,5-(CF)CH))D sta- ble at room temperature and formed by a one-electron- oxidation-induced intramolecular skeletal rearrangement re- action. Such a species has been validated by electron para- magnetic resonance (EPR) spectroscopy, single-crystal X-ray diffraction, UV/Vis spectroscopy and density functional theory (DFT) calculations Compound 3(BARF) exhibits a large majority of spin density at a two-coordinate phosphorus atom (0.74 a.u.) and a cationic charge located predominantly at the four-coordinate phosphorus atom (1.53 a.u.), which are sepa- rated by one carbon atom. This species represents an isolable entity of a phosphorus radical cation that is the closest to a genuine phosphorus DRC to date.

carbenes dicarbondiphosphide distonic radical cations phosphorus radicals

EI

English

NI Journal Papers

Others

20223412618038

Atoms ; Density functional theory ; Electron spin resonance spectroscopy ; Mass spectrometry ; Positive ions ; Room temperature ; Single crystals ; Ultraviolet visible spectroscopy

Thermodynamics:641.1 ; Chemistry:801 ; Chemical Products Generally:804 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Crystalline Solids:933.1

MATERIALS SCIENCE

2-s2.0-85136194821

Scopus

1.College of Chemistry and Materials Science,Jinan University Guangzhou,510632,China
2.Shenzhen Grubbs Institute and Department of Chemistry,Southern University of Science and Technology Shenzhen,Shenzhen,518055,China
3.Lehn Institute of Functional Materials (LIFM),School of Chemistry,Sun Yat-Sen University Guangzhou,510275,China
4.State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin,30071,China
5.Department of Chemistry and Applied Biosciences,ETH Zfrich Vladimir-Prelog-Weg 1,Zfrich,8093,Switzerland

Chen，Xiaodan,Liu，Liu Leo,Liu，Shihua,et al. A Room-Temperature Stable Distonic Radical Cation[J]. ADVANCED MATERIALS,2020,132(52):24038-24043.

Chen，Xiaodan,Liu，Liu Leo,Liu，Shihua,Grützmacher，Hansjörg,&Li，Zhongshu.(2020).A Room-Temperature Stable Distonic Radical Cation.ADVANCED MATERIALS,132(52),24038-24043.

Chen，Xiaodan,et al."A Room-Temperature Stable Distonic Radical Cation".ADVANCED MATERIALS 132.52(2020):24038-24043.