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Inorganics 2017, 5(3), 48; doi:10.3390/inorganics5030048

Synthesis, Crystal Structures and Magnetic Properties of Composites Incorporating an Fe(II) Spin Crossover Complex and Polyoxometalates

Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba 305-8571, Japan
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK
Author to whom correspondence should be addressed.
Received: 30 June 2017 / Revised: 18 July 2017 / Accepted: 19 July 2017 / Published: 22 July 2017
(This article belongs to the Special Issue Spin-Crossover Complexes)
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[Fe(dppOH)2]2+ (dppOH = 2,6-di(pyrazol-1-yl)-4-(hydroxymethyl)pyridine) is known to show spin crossover (SCO) behavior and light-induced excited spin state transitions (LIESST). Here, we show that the SCO properties of the [Fe(dppOH)2]2+ complex can be altered by a crystal engineering approach employing counter anion exchange with polyoxometalate (POM) anions. Using this strategy, two new composite materials (TBA)[Fe(dppOH)2][PMo12O40] (1) and [Fe(dppOH)2]3[PMo12O40]2 (2) (TBA = tetra-n-butylammonium) have been isolated and studied by single crystal X-ray diffraction and magnetic susceptibility measurements. 1 was found to be in a high spin state at 300 K and showed no spin crossover behavior due to a dense packing structure induced by hydrogen bonding between the hydroxyl group of the dppOH ligands and the POM anions. Conversely, 2 contains two crystallographically unique Fe centers, where one is in the low spin state whilst the other is locked in a high spin state in a manner analogous to 1. As a result, 2 was found to show partial spin crossover behavior around 230 K with a decrease in the χmT value of 1.9 emu·mol−1·K. This simple approach could therefore provide a useful method to aid in the design of next generation spin crossover materials. View Full-Text
Keywords: spin crossover; polyoxometalate; crystal engineering; magnetic properties; iron spin crossover; polyoxometalate; crystal engineering; magnetic properties; iron

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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Kuramochi, S.; Shiga, T.; Cameron, J.M.; Newton, G.N.; Oshio, H. Synthesis, Crystal Structures and Magnetic Properties of Composites Incorporating an Fe(II) Spin Crossover Complex and Polyoxometalates. Inorganics 2017, 5, 48.

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