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

[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 emplo...

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Main Authors: Kuramochi, Satoshi, Shiga, Takuya, Cameron, Jamie M., Newton, Graham N., Oshio, Hiroki
Format: Article
Published: MDPI 2017
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Online Access:https://eprints.nottingham.ac.uk/44459/
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author Kuramochi, Satoshi
Shiga, Takuya
Cameron, Jamie M.
Newton, Graham N.
Oshio, Hiroki
author_facet Kuramochi, Satoshi
Shiga, Takuya
Cameron, Jamie M.
Newton, Graham N.
Oshio, Hiroki
author_sort Kuramochi, Satoshi
building Nottingham Research Data Repository
collection Online Access
description [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.
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spelling nottingham-444592020-05-04T18:56:36Z https://eprints.nottingham.ac.uk/44459/ 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 [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. MDPI 2017-07-22 Article PeerReviewed Kuramochi, Satoshi, Shiga, Takuya, Cameron, Jamie M., Newton, Graham N. and Oshio, Hiroki (2017) Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates. Inorganics, 5 (3). 48/1-48/8. ISSN 2304-6740 Spin crossover; Polyoxometalate; Crystal engineering; Magnetic properties; Iron http://www.mdpi.com/2304-6740/5/3/48 doi:10.3390/inorganics5030048 doi:10.3390/inorganics5030048
spellingShingle Spin crossover; Polyoxometalate; Crystal engineering; Magnetic properties; Iron
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
title Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates
title_full Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates
title_fullStr Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates
title_full_unstemmed Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates
title_short Synthesis, crystal structures and magnetic properties of composites incorporating an Fe(II) spin crossover complex and polyoxometalates
title_sort synthesis, crystal structures and magnetic properties of composites incorporating an fe(ii) spin crossover complex and polyoxometalates
topic Spin crossover; Polyoxometalate; Crystal engineering; Magnetic properties; Iron
url https://eprints.nottingham.ac.uk/44459/
https://eprints.nottingham.ac.uk/44459/
https://eprints.nottingham.ac.uk/44459/