通过在固态氩中光解2,4,6-三叠氮基-3-氰基-5-氟吡啶得到的多组分、多自旋分子体系的电子顺磁共振光谱。

EPR spectroscopy of multicomponent, multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon.

作者信息

Chapyshev Sergei V, Korchagin Denis V, Grote Dirk, Sander Wolfram

机构信息

Department of Nanophotonics, Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia.

Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, Bochum, Germany.

出版信息

Magn Reson Chem. 2019 Aug;57(8):472-478. doi: 10.1002/mrc.4877. Epub 2019 Jun 3.

DOI:10.1002/mrc.4877

PMID:30997697

Abstract

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (D = 1.000 cm , E = 0), triplet 2,4-diazido-3-cyano-5-fluoropyridyl-2-nitrene (D = 1.043 cm , E = 0), triplet 2,6-diazido-3-cyano-5-fluoropyridyl-4-nitrene (D = 1.128 cm , E = 0 cm ), quintet 4-azido-3-cyano-5-fluoropyridyl-2,6-dinitrene (D = 0.211 cm , E = 0.0532 cm ), quintet 2-azido-3-cyano-5-fluoropyridyl-4,6-dinitrene (D = 0.208 cm , E = 0.0386 cm ), and septet 3-cyano-5-fluoropyridyl-2,4,6-trinitrene (D = -0.1017 cm , E = -0.0042 cm ) in a 38:4:7:22:14:4 ratio, respectively.

摘要

通过在固态氩中光解2,4,6-三叠氮基-3-氰基-5-氟吡啶，得到了由一个七重态三氮烯、两个五重态二氮烯和三个三重态单氮烯组成的复杂多组分、多自旋分子体系。为了鉴定这些顺磁性产物，采用了电子顺磁共振光谱结合线形光谱模拟和密度泛函理论计算的方法。发现光解产物分别是三重态2,4-二叠氮基-3-氰基-5-氟吡啶基-6-氮烯（D = 1.000 cm，E = 0）、三重态2,4-二叠氮基-3-氰基-5-氟吡啶基-2-氮烯（D = 1.043 cm，E = 0）、三重态2,6-二叠氮基-3-氰基-5-氟吡啶基-4-氮烯（D = 1.128 cm，E = 0 cm）、五重态4-叠氮基-3-氰基-5-氟吡啶基-2,6-二氮烯（D = 0.211 cm，E = 0.0532 cm）、五重态2-叠氮基-3-氰基-5-氟吡啶基-4,6-二氮烯（D = 0.208 cm，E = 0.0386 cm）和七重态3-氰基-5-氟吡啶基-2,4,6-三氮烯（D = -0.1017 cm，E = -0.0042 cm），其比例为38:4:7:22:14:4。