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

Nikolay A. Semenov; Ekaterina A. Radiush; Elena A. Chulanova; Alexandra M. Z. Slawin; J. Derek Woollins; Evgeny M. Kadilenko; Irina Yu Bagryanskaya; Irina G. Irtegova; Artem S. Bogomyakov; Leonid A. Shundrin; Nina P. Gritsan; Andrey Zibarev

doi:10.1039/c9nj04069b

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

Nikolay A. Semenov^*
, Ekaterina A. Radiush
, Elena A. Chulanova
, Alexandra M. Z. Slawin
, J. Derek Woollins
, Evgeny M. Kadilenko
, Irina Yu Bagryanskaya
, Irina G. Irtegova
, Artem S. Bogomyakov
, Leonid A. Shundrin
, Nina P. Gritsan
, Andrey Zibarev

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

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 π-dimers of [1]˙⁻ featuring a shortened interplanar separation of 3.18 Å, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the π-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.

Original language	English
Pages (from-to)	16331-16337
Number of pages	7
Journal	New Journal of Chemistry
Volume	43
Issue number	41
Early online date	12 Sept 2019
DOIs	https://doi.org/10.1039/c9nj04069b
Publication status	Published - 7 Nov 2019

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Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts (dataset)
Semenov, N. A. (Creator), Radiush, E. A. (Creator), Chulanova, E. A. (Creator), Slawin, A. M. Z. (Creator), Woollins, J. D. (Creator), Kadilenko, E. M. (Creator), Bagryanskaya, I. Y. (Creator), Irtegova, I. G. (Creator), Bogomyakov, A. S. (Creator), Shundrin, L. A. (Creator), Gritsan, N. P. (Creator) & Zibarev, A. (Creator), Cambridge Crystallographic Data Centre, 2019
https://dx.doi.org/10.5517/ccdc.csd.cc22ckpq and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc22ckqr, https://dx.doi.org/10.5517/ccdc.csd.cc22ckrs, https://dx.doi.org/10.5517/ccdc.csd.cc22ckst (show fewer)
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Semenov, N. A., Radiush, E. A., Chulanova, E. A., Slawin, A. M. Z., Woollins, J. D., Kadilenko, E. M., Bagryanskaya, I. Y., Irtegova, I. G., Bogomyakov, A. S., Shundrin, L. A., Gritsan, N. P., & Zibarev, A. (2019). Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts. New Journal of Chemistry, 43(41), 16331-16337. https://doi.org/10.1039/c9nj04069b

@article{2bc6911c3b464917bed6b0261a0b7b04,

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

abstract = "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 π-dimers of [1]˙− featuring a shortened interplanar separation of 3.18 {\AA}, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the π-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.",

author = "Semenov, \{Nikolay A.\} and Radiush, \{Ekaterina A.\} and Chulanova, \{Elena A.\} and Slawin, \{Alexandra M. Z.\} and Woollins, \{J. Derek\} and Kadilenko, \{Evgeny M.\} and Bagryanskaya, \{Irina Yu\} and Irtegova, \{Irina G.\} and Bogomyakov, \{Artem S.\} and Shundrin, \{Leonid A.\} and Gritsan, \{Nina P.\} and Andrey Zibarev",

note = "N. A. S. and E. A. R. acknowledge the Russian Science Foundation for the financial support (project no. 18-73-00225). N. P. G. and E. M. K. acknowledge the Ministry of Science and Higher Education of the Russian Federation (project no. 0304-2017-0008) for financial support of the computational part of this work and the Irkutsk Supercomputer Centre of the Siberian Branch of the Russian Academy of Sciences52 for computational resources. ",

year = "2019",

month = nov,

day = "7",

doi = "10.1039/c9nj04069b",

language = "English",

volume = "43",

pages = "16331--16337",

journal = "New Journal of Chemistry",

issn = "1144-0546",

publisher = "Royal Society of Chemistry",

number = "41",

}

Semenov, NA, Radiush, EA, Chulanova, EA, Slawin, AMZ, Woollins, JD, Kadilenko, EM, Bagryanskaya, IY, Irtegova, IG, Bogomyakov, AS, Shundrin, LA, Gritsan, NP & Zibarev, A 2019, 'Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts', New Journal of Chemistry, vol. 43, no. 41, pp. 16331-16337. https://doi.org/10.1039/c9nj04069b

TY - JOUR

T1 - Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts

AU - Semenov, Nikolay A.

AU - Radiush, Ekaterina A.

AU - Chulanova, Elena A.

AU - Slawin, Alexandra M. Z.

AU - Woollins, J. Derek

AU - Kadilenko, Evgeny M.

AU - Bagryanskaya, Irina Yu

AU - Irtegova, Irina G.

AU - Bogomyakov, Artem S.

AU - Shundrin, Leonid A.

AU - Gritsan, Nina P.

AU - Zibarev, Andrey

N1 - N. A. S. and E. A. R. acknowledge the Russian Science Foundation for the financial support (project no. 18-73-00225). N. P. G. and E. M. K. acknowledge the Ministry of Science and Higher Education of the Russian Federation (project no. 0304-2017-0008) for financial support of the computational part of this work and the Irkutsk Supercomputer Centre of the Siberian Branch of the Russian Academy of Sciences52 for computational resources.

PY - 2019/11/7

Y1 - 2019/11/7

N2 - 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 π-dimers of [1]˙− featuring a shortened interplanar separation of 3.18 Å, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the π-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.

AB - 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 π-dimers of [1]˙− featuring a shortened interplanar separation of 3.18 Å, and that of 3 showed chains of alternating cations and anions. DFT and CASSCF calculations on the π-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.

U2 - 10.1039/c9nj04069b

DO - 10.1039/c9nj04069b

M3 - Article

SN - 1144-0546

VL - 43

SP - 16331

EP - 16337

JO - New Journal of Chemistry

JF - New Journal of Chemistry

IS - 41

ER -

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

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

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