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 -