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Modulation of Mn3+ Spin State by Guest Molecule Inclusion

School of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, Ireland
School of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN, UK
Author to whom correspondence should be addressed.
Present address: FZU-Institute of Physics-Czech Academy of Sciences, Na Slovance 1999/2, 182 21 Prague 8, Czech Republic.
Academic Editor: Sergey G. Ovchinnikov
Molecules 2020, 25(23), 5603;
Received: 10 November 2020 / Revised: 25 November 2020 / Accepted: 26 November 2020 / Published: 28 November 2020
(This article belongs to the Special Issue Spin Crossover (SCO) Research 2020)
Spin state preferences for a cationic Mn3+ chelate complex in four different crystal lattices are investigated by crystallography and SQUID magnetometry. The [MnL1]+ complex cation was prepared by complexation of Mn3+ to the Schiff base chelate formed from condensation of 4-methoxysalicylaldehyde and 1,2-bis(3-aminopropylamino)ethane. The cation was crystallized separately with three polyatomic counterions and in one case was found to cocrystallize with a percentage of unreacted 4-methoxysalicylaldehyde starting material. The spin state preferences of the four resultant complexes [MnL1]CF3SO3·xH2O, (1), [MnL1]PF6·xH2O, (2), [MnL1]PF6·xsal·xH2O, (2b), and [MnL1]BPh4, (3), were dependent on their ability to form strong intermolecular interactions. Complexes (1) and (2), which formed hydrogen bonds between [MnL1]+, lattice water and in one case also with counterion, showed an incomplete thermal spin crossover over the temperature range 5–300 K. In contrast, complex (3) with the BPh4, counterion and no lattice water, was locked into the high spin state over the same temperature range, as was complex (2b), where inclusion of the 4-methoxysalicylaldehyde guest blocked the H-bonding interaction. View Full-Text
Keywords: spin crossover; Mn3+; Schiff base; hexadentate; supramolecular; guest inclusion spin crossover; Mn3+; Schiff base; hexadentate; supramolecular; guest inclusion
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MDPI and ACS Style

Kühne, I.A.; Esien, K.; Gavin, L.C.; Müller-Bunz, H.; Felton, S.; Morgan, G.G. Modulation of Mn3+ Spin State by Guest Molecule Inclusion. Molecules 2020, 25, 5603.

AMA Style

Kühne IA, Esien K, Gavin LC, Müller-Bunz H, Felton S, Morgan GG. Modulation of Mn3+ Spin State by Guest Molecule Inclusion. Molecules. 2020; 25(23):5603.

Chicago/Turabian Style

Kühne, Irina A., Kane Esien, Laurence C. Gavin, Helge Müller-Bunz, Solveig Felton, and Grace G. Morgan 2020. "Modulation of Mn3+ Spin State by Guest Molecule Inclusion" Molecules 25, no. 23: 5603.

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