Solvatomorphism and anion effects in fluorinated MnIII spin crossover complexes

Conor T. Kelly; Vibe Boel Jakobsen; Aizuddin Sultan; Ross Jordan; Brendan Twamley; Peter Nockemann; Solveig Felton; Helge Müller-Bunz; Grace Genevieve Morgan

doi:10.1002/ejic.202400796

Solvatomorphism and anion effects in fluorinated Mn^III spin crossover complexes

Conor T. Kelly^*
, Vibe Boel Jakobsen
, Aizuddin Sultan
, Ross Jordan
, Brendan Twamley
, Peter Nockemann
, Solveig Felton
, Helge Müller-Bunz
, Grace Genevieve Morgan^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Eight new Mn^III salts of the [Mn^III(3,5-diF-sal₂323)]X complex are reported, of which four show thermal spin crossover (SCO): 1a [Mn^III(3,5-diF-sal₂323)]PF₆·0.33CH₃CN, 1b [Mn^III(3,5-diF-sal₂323)]PF₆·CH₃CN, 1c [Mn^III(3,5-diF-sal₂323)]PF₆, 2 [Mn^III(3,5-diF-sal₂323)]AsF6, 3 [MnIII(3,5-diF-sal₂323)]NO₃, 4 [Mn^III(3,5-diF-sal₂323)]Br, 5 [Mn^III(3,5-diF-sal₂323)]BF₄, and 6 [Mn^III(3,5-diF-sal₂323)]OTf·0.66H₂O. Solvatomorphism is observed in the PF₆⁻ salt, revealing one complex which undergoes gradual SCO (1a·0.33CH₃CN), one that is fully high spin (1b·CH₃CN); a third solvent-free solvatomorph 1c is also recovered where structural data indicate a spin triplet at 100 K. In 1a, three independent Mn^III sites with spin state ordering of HS:LS:LS at 100 K and HS:IS:IS at 293 K are observed, where HS = high spin (S = 2), LS = low spin (S = 1), and IS = intermediate spin (i.e., an equilibrium of S = 1 and S = 2). Structural data are presented for all complexes, and magnetic data for 1a, 1b, 2, and 3.

Original language	English
Article number	e202400796
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	28
Issue number	15
Early online date	20 May 2025
DOIs	https://doi.org/10.1002/ejic.202400796
Publication status	Published - 28 May 2025

Keywords

electronic structures
magnetic properties
N,O ligands
polymorphism
spin crossover

ASJC Scopus subject areas

Inorganic Chemistry

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Cite this

@article{33c63f87fd544c5eafef1971c858fab9,

title = "Solvatomorphism and anion effects in fluorinated MnIII spin crossover complexes",

abstract = "Eight new MnIII salts of the [MnIII(3,5-diF-sal2323)]X complex are reported, of which four show thermal spin crossover (SCO): 1a [MnIII(3,5-diF-sal2323)]PF6·0.33CH3CN, 1b [MnIII(3,5-diF-sal2323)]PF6·CH3CN, 1c [MnIII(3,5-diF-sal2323)]PF6, 2 [MnIII(3,5-diF-sal2323)]AsF6, 3 [MnIII(3,5-diF-sal2323)]NO3, 4 [MnIII(3,5-diF-sal2323)]Br, 5 [MnIII(3,5-diF-sal2323)]BF4, and 6 [MnIII(3,5-diF-sal2323)]OTf·0.66H2O. Solvatomorphism is observed in the PF6− salt, revealing one complex which undergoes gradual SCO (1a·0.33CH3CN), one that is fully high spin (1b·CH3CN); a third solvent-free solvatomorph 1c is also recovered where structural data indicate a spin triplet at 100 K. In 1a, three independent MnIII sites with spin state ordering of HS:LS:LS at 100 K and HS:IS:IS at 293 K are observed, where HS = high spin (S = 2), LS = low spin (S = 1), and IS = intermediate spin (i.e., an equilibrium of S = 1 and S = 2). Structural data are presented for all complexes, and magnetic data for 1a, 1b, 2, and 3.",

keywords = "electronic structures, magnetic properties, N,O ligands, polymorphism, spin crossover",

author = "Kelly, \{Conor T.\} and Jakobsen, \{Vibe Boel\} and Aizuddin Sultan and Ross Jordan and Brendan Twamley and Peter Nockemann and Solveig Felton and Helge M{\"u}ller-Bunz and Morgan, \{Grace Genevieve\}",

year = "2025",

month = may,

day = "28",

doi = "10.1002/ejic.202400796",

language = "English",

volume = "28",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "15",

}

TY - JOUR

T1 - Solvatomorphism and anion effects in fluorinated MnIII spin crossover complexes

AU - Kelly, Conor T.

AU - Jakobsen, Vibe Boel

AU - Sultan, Aizuddin

AU - Jordan, Ross

AU - Twamley, Brendan

AU - Nockemann, Peter

AU - Felton, Solveig

AU - Müller-Bunz, Helge

AU - Morgan, Grace Genevieve

PY - 2025/5/28

Y1 - 2025/5/28

N2 - Eight new MnIII salts of the [MnIII(3,5-diF-sal2323)]X complex are reported, of which four show thermal spin crossover (SCO): 1a [MnIII(3,5-diF-sal2323)]PF6·0.33CH3CN, 1b [MnIII(3,5-diF-sal2323)]PF6·CH3CN, 1c [MnIII(3,5-diF-sal2323)]PF6, 2 [MnIII(3,5-diF-sal2323)]AsF6, 3 [MnIII(3,5-diF-sal2323)]NO3, 4 [MnIII(3,5-diF-sal2323)]Br, 5 [MnIII(3,5-diF-sal2323)]BF4, and 6 [MnIII(3,5-diF-sal2323)]OTf·0.66H2O. Solvatomorphism is observed in the PF6− salt, revealing one complex which undergoes gradual SCO (1a·0.33CH3CN), one that is fully high spin (1b·CH3CN); a third solvent-free solvatomorph 1c is also recovered where structural data indicate a spin triplet at 100 K. In 1a, three independent MnIII sites with spin state ordering of HS:LS:LS at 100 K and HS:IS:IS at 293 K are observed, where HS = high spin (S = 2), LS = low spin (S = 1), and IS = intermediate spin (i.e., an equilibrium of S = 1 and S = 2). Structural data are presented for all complexes, and magnetic data for 1a, 1b, 2, and 3.

AB - Eight new MnIII salts of the [MnIII(3,5-diF-sal2323)]X complex are reported, of which four show thermal spin crossover (SCO): 1a [MnIII(3,5-diF-sal2323)]PF6·0.33CH3CN, 1b [MnIII(3,5-diF-sal2323)]PF6·CH3CN, 1c [MnIII(3,5-diF-sal2323)]PF6, 2 [MnIII(3,5-diF-sal2323)]AsF6, 3 [MnIII(3,5-diF-sal2323)]NO3, 4 [MnIII(3,5-diF-sal2323)]Br, 5 [MnIII(3,5-diF-sal2323)]BF4, and 6 [MnIII(3,5-diF-sal2323)]OTf·0.66H2O. Solvatomorphism is observed in the PF6− salt, revealing one complex which undergoes gradual SCO (1a·0.33CH3CN), one that is fully high spin (1b·CH3CN); a third solvent-free solvatomorph 1c is also recovered where structural data indicate a spin triplet at 100 K. In 1a, three independent MnIII sites with spin state ordering of HS:LS:LS at 100 K and HS:IS:IS at 293 K are observed, where HS = high spin (S = 2), LS = low spin (S = 1), and IS = intermediate spin (i.e., an equilibrium of S = 1 and S = 2). Structural data are presented for all complexes, and magnetic data for 1a, 1b, 2, and 3.

KW - electronic structures

KW - magnetic properties

KW - N,O ligands

KW - polymorphism

KW - spin crossover

U2 - 10.1002/ejic.202400796

DO - 10.1002/ejic.202400796

M3 - Article

AN - SCOPUS:105005530932

SN - 1434-1948

VL - 28

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 15

M1 - e202400796

ER -