Neutron Studies of a High Spin Fe<sub>19</sub> Molecular Nanodisc

The molecular cluster system [Fe<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>19</mn></msub></semantics></math></inline-formula>(metheidi)...

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Bibliographic Details
Main Authors: Francis L. Pratt, Tatiana Guidi, Pascal Manuel, Christopher E. Anson, Jinkui Tang, Stephen J. Blundell, Annie K. Powell
Format: Article
Language:English
Published: MDPI AG 2021-05-01
Series:Magnetochemistry
Subjects:
Online Access:https://www.mdpi.com/2312-7481/7/6/74
Description
Summary:The molecular cluster system [Fe<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>19</mn></msub></semantics></math></inline-formula>(metheidi)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>10</mn></msub></semantics></math></inline-formula>(OH)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>14</mn></msub></semantics></math></inline-formula>O<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>6</mn></msub></semantics></math></inline-formula>(H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>O)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>12</mn></msub></semantics></math></inline-formula>]NO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>·24H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>O, abbreviated as Fe<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>19</mn></msub></semantics></math></inline-formula>, contains nineteen Fe(III) ions arranged in a disc-like structure with the total spin <i>S</i> = 35/2. For the first order, it behaves magnetically as a single molecule magnet with a 16 K anisotropy barrier. The high spin value enhances weak intermolecular interactions for both dipolar and superexchange mechanisms and an eventual transition to antiferromagnetic order occurs at 1.2 K. We used neutron diffraction to determine both the mode of ordering and the easy spin axis. The observed ordering was not consistent with a purely dipolar driven order, indicating a significant contribution from intermolecular superexchange. The easy axis is close to the molecular Fe1–Fe10 axis. Inelastic neutron scattering was used to follow the magnetic order parameter and to measure the magnetic excitations. Direct transitions to at least three excited states were found in the 2 to 3 meV region. Measurements below 0.2 meV revealed two low energy excited states, which were assigned to <i>S</i> = 39/2 and <i>S</i> = 31/2 spin states with respective excitation gaps of 1.5 and 3 K. Exchange interactions operating over distances of order 10 Å were determined to be on the order of 5 mK and were eight-times stronger than the dipolar coupling.
ISSN:2312-7481