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Systematic Design of Crystal Structure for Hofmann-Like Spin Crossover Fe(L)2[Ag(CN)2]2 Complexes

1
Department of Science and Engineering, Graduate School of Science and Engineering, Tokyo Denki University, Hatoyama, Hiki-gun, Saitama 350-0394, Japan
2
Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan
3
Department of Creative Technology Engineering Course of Chemical Engineering, Anan College, 265 Aoki, Minobayashi, Anan, Tokushima 774-0017, Japan
4
Department of Physics, Faculty of Science, Toho University, 2-2-1, Miyama 274-8510, Japan
*
Author to whom correspondence should be addressed.
Crystals 2019, 9(7), 370; https://doi.org/10.3390/cryst9070370
Received: 7 June 2019 / Revised: 10 July 2019 / Accepted: 11 July 2019 / Published: 20 July 2019
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Abstract

The synthesis, crystal structures, and magnetic properties of a new two-dimensional (2D) Hofmann-like series, FeII(L)2[AgI(CN)2]2 (L = 3-cyano-4-methylpyridine (1), allyl isonicotinate (2), phenyl-isonicotinate (3), and benzyl nicotinate (4)) were studied. These compounds have a 2D sheet structure because of their strongly determinate self-assembly process. An octahedral FeII ion is coordinated with the nitrogen atoms of[AgI(CN)2 linear units at equatorial positions and monodentate pyridine derivatives at the axial position. The layers construct a parallel stacking array. Compounds 13 show pairs of layers constructed by intermetallic Ag···Ag interactions. Compound 4 shows a mono-layer structure. The substituent bulk of the ligands affects the interlayer space. Compounds 14 undergo a 100% spin transition. However, compound 1, incorporating a smaller group, has a relatively lower critical temperature (Tc = 182 K (1), Tc = 221 K (2), Tc = 227 (3) and Tc1 = 236 K, Tc2 = 215 K (4)). We investigated the correlations between our systematic crystal design, substituent size, and the spin crossover profiles. View Full-Text
Keywords: coordination polymer; intermetallic interaction; cooperative interaction; crystal engineering coordination polymer; intermetallic interaction; cooperative interaction; crystal engineering
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Kosone, T.; Makido, Y.; Okuda, S.; Haigo, A.; Kawasaki, T.; Akahoshi, D.; Saito, T.; Kitazawa, T. Systematic Design of Crystal Structure for Hofmann-Like Spin Crossover Fe(L)2[Ag(CN)2]2 Complexes. Crystals 2019, 9, 370.

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