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Evolution of Spin-Crossover Transition in Hybrid Crystals Involving Cationic Iron Complexes [Fe(III)(3-OMesal2-trien)]+ and Anionic Gold Bis(dithiolene) Complexes Au(dmit)2 and Au(dddt)2

1
Institute of Problems of Chemical Physics, RAS, Chernogolovka, MD 142432, Russia
2
M.N. Miheev Institute of Metal Physics, Ural Branch of Russian Academy of Sciences, S. Kovalevskaya str., 18, Yekaterinburg 620137, Russia
3
Laboratory of Physics, Lappeenranta University of Technology, Box 20, FI-53851 Lappeenranta, Finland
4
Institute of Solid State Physics, RAS, Chernogolovka, MD 142432, Russia
5
Faculty of Fundamental Physical and Chemical Engineering MGU, Moscow, MOS 119991, Russia
*
Authors to whom correspondence should be addressed.
Crystals 2018, 8(10), 382; https://doi.org/10.3390/cryst8100382
Received: 17 September 2018 / Revised: 26 September 2018 / Accepted: 27 September 2018 / Published: 3 October 2018
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
Hybrid ion-pair crystals involving hexadentate [Fe(III)(3-OMesal2-trien)]+ spin-crossover (SCO) cationic complexes and anionic gold complexes [Au(dmit)2] (1) (dmit = 4,5-dithiolato-1,3-dithiole-2-thione) and [Au(dddt)2] (2) (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) were synthesized and studied by single-crystal X-ray diffraction, P-XRD, and SQUID magnetometry. Our study shows that both complexes have similar 1:1 stoichiometry but different symmetry and crystal packing. Complex 1 has a rigid structure in which the SCO cations are engaged in strong π-interplay with molecular surrounding and does not show SCO transition while 2 demonstrates a reversible transition at Tsco = 118 K in a much “softer”, hydrogen-bonded structure. A new structural indicator of spin state in [Fe(sal2-trien)]+ complexes based on conformational analysis has been proposed. Aging and thermocycling ruined the SCO transition increasing the residual HS fraction from 14 to 41%. Magnetic response of 1 is explained by the AFM coupled dimers S = 5/2 with J1 = −0.18 cm−1. Residual high-spin fraction of 2, apart from a contribution of the weak dimers with J12 = J34 = −0.29 cm−1, is characterized by a stronger interdimer coupling of J23 = −1.69 cm−1, which is discussed in terms of possible involvement of neutral radicals [Au(dddt)2]. View Full-Text
Keywords: metal dithiolene complexes; [Au(dmit)2], [Au(dddt)2]; ion-pair crystals; [Fe(III)(3-OMesal2-trien)]+; coordination complexes; crystal structure; magnetic properties; magnetic susceptibility; magnetization; spin-crossover transition metal dithiolene complexes; [Au(dmit)2], [Au(dddt)2]; ion-pair crystals; [Fe(III)(3-OMesal2-trien)]+; coordination complexes; crystal structure; magnetic properties; magnetic susceptibility; magnetization; spin-crossover transition
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MDPI and ACS Style

Spitsyna, N.G.; Shvachko, Y.N.; Starichenko, D.V.; Lahderanta, E.; Komlev, A.A.; Zorina, L.V.; Simonov, S.V.; Blagov, M.A.; Yagubskii, E.B. Evolution of Spin-Crossover Transition in Hybrid Crystals Involving Cationic Iron Complexes [Fe(III)(3-OMesal2-trien)]+ and Anionic Gold Bis(dithiolene) Complexes Au(dmit)2 and Au(dddt)2. Crystals 2018, 8, 382. https://doi.org/10.3390/cryst8100382

AMA Style

Spitsyna NG, Shvachko YN, Starichenko DV, Lahderanta E, Komlev AA, Zorina LV, Simonov SV, Blagov MA, Yagubskii EB. Evolution of Spin-Crossover Transition in Hybrid Crystals Involving Cationic Iron Complexes [Fe(III)(3-OMesal2-trien)]+ and Anionic Gold Bis(dithiolene) Complexes Au(dmit)2 and Au(dddt)2. Crystals. 2018; 8(10):382. https://doi.org/10.3390/cryst8100382

Chicago/Turabian Style

Spitsyna, Nataliya G., Yuri N. Shvachko, Denis V. Starichenko, Erkki Lahderanta, Anton A. Komlev, Leokadiya V. Zorina, Sergey V. Simonov, Maksim A. Blagov, and Eduard B. Yagubskii 2018. "Evolution of Spin-Crossover Transition in Hybrid Crystals Involving Cationic Iron Complexes [Fe(III)(3-OMesal2-trien)]+ and Anionic Gold Bis(dithiolene) Complexes Au(dmit)2 and Au(dddt)2" Crystals 8, no. 10: 382. https://doi.org/10.3390/cryst8100382

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