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Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates

Kuramochi, Satoshi; Shiga, Takuya; Cameron, Jamie M.; Newton, Graham N.; Oshio, Hiroki

Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates Thumbnail


Authors

Satoshi Kuramochi

Takuya Shiga

Jamie M. Cameron

Hiroki Oshio



Abstract

[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 is found to be in a high spin state at 300 K and shows 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 is 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.

Journal Article Type Article
Acceptance Date Jul 19, 2017
Publication Date Jul 22, 2017
Deposit Date Jul 28, 2017
Publicly Available Date Jul 28, 2017
Journal Inorganics
Electronic ISSN 2304-6740
Publisher MDPI
Peer Reviewed Peer Reviewed
Volume 5
Issue 3
Article Number 48
DOI https://doi.org/10.3390/inorganics5030048
Keywords Spin crossover; Polyoxometalate; Crystal engineering; Magnetic properties; Iron
Public URL https://nottingham-repository.worktribe.com/output/873809
Publisher URL http://www.mdpi.com/2304-6740/5/3/48

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