Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts

被引：11

作者：

Semenov, Nikolay A. ^{[1
]}

Radiush, Ekaterina A. ^{[1
]}

Chulanova, Elena A. ^{[1
,2
]}

Slawin, Alexandra M. Z. ^{[3
]}

Woollins, J. Derek ^{[4
]}

Kadilenko, Evgeny M. ^{[2
,5
]}

Bagryanskaya, Irina Yu ^{[1
]}

Irtegova, Irina G. ^{[1
]}

Bogomyakov, Artem S. ^{[2
,6
]}

Shundrin, Leonid A. ^{[1
,2
]}

Gritsan, Nina P. ^{[5
,7
]}

Zibarev, Andrey, V ^{[1
,7
]}

机构：

[1] Russian Acad Sci, Siberian Branch, Inst Organ Chem, Novosibirsk 630090, Russia

[2] Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia

[3] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[4] Khalifa Univ, Dept Chem, Abu Dhabi, U Arab Emirates

[5] Russian Acad Sci, Siberian Branch, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia

[6] Russian Acad Sci, Siberian Branch, Int Tomog Ctr, Novosibirsk 630090, Russia

[7] Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia

来源：

NEW JOURNAL OF CHEMISTRY | 2019年 / 43卷 / 41期

基金：

俄罗斯科学基金会;

关键词：

STATE PERTURBATION-THEORY; RADICAL-ANION SALTS; CRYSTAL-STRUCTURE; HETEROSPIN S-1; VALENCE; IMPLEMENTATION;

D O I：

10.1039/c9nj04069b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

5,6-Dicyano[1,2,5]selenadiazolo[3,4-b]pyrazine 1 was synthesized and electrochemically and chemically reduced into its radical anion [1](-), which was characterized by EPR spectroscopy and DFT calculations, and isolated in the form of homospin salts [K(18-crown-6)](+)[1](-) (2) and [Na(18-crown-6)](+)[1](-) (3). The crystal structure of 2 revealed pi-dimers of [1](-) featuring a shortened interplanar separation of 3.18 angstrom, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the pi-dimers of [1](-) suggest a closed-shell singlet ground state with a noticeable contribution of diradical character. According to EPR and SQUID magnetometry, salt 2 is diamagnetic in the range of 2-300 K, whereas salt 3 is paramagnetic and reveals weak antiferromagnetic exchange interactions.

引用

页码：16331 / 16337

页数：7

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