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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.; Shvachko, Yuri N.; Starichenko, Denis V.; Lahderanta, Erkki; Komlev, Anton A.; Zorina, Leokadiya V.; Simonov, Sergey V.; Blagov, Maksim A.; Yagubskii, Eduard B. 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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