Unveiling the Relationship between Counterion Size and Spin Crossover Dynamics in Hexadentate Schiff-Base Manganese(III) Complexes

Abstract

Understanding the relationship between molecular packings/interactions and spin crossover property is essential for advancing solid-state molecular memory devices. In this work, a series of hexadentate Schiff base manganese (III) complexes [Mn(4F-sal2323)]X, X = ClO4 (1); X = AsF6 (2); X = PF6 (3); X = ReO4 (4) and X = NO3 (5) were synthesized and characterized. Magnetic studies showed that complex 1 exhibited an abrupt spin transition at 90 K with a 10 K-wide thermal hysteresis, while complexes 25 exhibited gradual and incomplete spin transition with no hysteresis. The Magneto-structural correlation analysis indicated that the SCO transition temperature is negatively correlated with the octahedral distortion and "void" space volume of anions. Detailed variable-temperature structural analysis revealed that hydrogen bonding interactions and close stackings hinder the torsional deformation of the MnIII coordination sphere, preventing complete SCO. Density-functional-theory (DFT) calculations revealed that the weaker hydrogen bonding in complex 1 led to lower atomic charges on the nitrogen atoms, thereby affecting the coordination field strength of the Mn center. This work demonstrates that the transition temperature of SCO is influenced by supramolecular stacking forces, and this relationship can be finely tuned by simply adjusting the size of the ions.

Supplementary files

Article information

Article type
Paper
Submitted
08 Jun 2025
Accepted
23 Jul 2025
First published
24 Jul 2025

Dalton Trans., 2025, Accepted Manuscript

Unveiling the Relationship between Counterion Size and Spin Crossover Dynamics in Hexadentate Schiff-Base Manganese(III) Complexes

M. Shang, D. Chen, R. Zhou, H. Lu, L. Ma, J. Xiao, L. Zhao, Y. Meng and T. Liu, Dalton Trans., 2025, Accepted Manuscript , DOI: 10.1039/D5DT01347J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements