Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion
Spin state preferences for a cationic Mn<sup>3+</sup> chelate complex in four different crystal lattices are investigated by crystallography and SQUID magnetometry. The [MnL<sub>1</sub>]<sup>+</sup> complex cation was prepared by complexation of Mn<sup>3+<...
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MDPI AG
2020-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/23/5603 |
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| author | Irina A. Kühne Kane Esien Laurence C. Gavin Helge Müller-Bunz Solveig Felton Grace G. Morgan |
| author_facet | Irina A. Kühne Kane Esien Laurence C. Gavin Helge Müller-Bunz Solveig Felton Grace G. Morgan |
| author_sort | Irina A. Kühne |
| collection | DOAJ |
| description | Spin state preferences for a cationic Mn<sup>3+</sup> chelate complex in four different crystal lattices are investigated by crystallography and SQUID magnetometry. The [MnL<sub>1</sub>]<sup>+</sup> complex cation was prepared by complexation of Mn<sup>3+</sup> 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 [MnL<sub>1</sub>]CF<sub>3</sub>SO<sub>3</sub>·xH<sub>2</sub>O, (<b>1</b>), [MnL<sub>1</sub>]PF<sub>6</sub>·xH<sub>2</sub>O, (<b>2</b>), [MnL<sub>1</sub>]PF<sub>6</sub>·xsal·xH<sub>2</sub>O, (<b>2b</b>), and [MnL<sub>1</sub>]BPh<sub>4</sub>, (<b>3</b>), were dependent on their ability to form strong intermolecular interactions. Complexes (<b>1</b>) and (<b>2</b>), which formed hydrogen bonds between [MnL<sub>1</sub>]<sup>+</sup>, 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 (<b>3</b>) with the BPh<sub>4</sub><sup>−</sup>, counterion and no lattice water, was locked into the high spin state over the same temperature range, as was complex (<b>2b</b>), where inclusion of the 4-methoxysalicylaldehyde guest blocked the H-bonding interaction. |
| first_indexed | 2024-03-10T14:29:30Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T14:29:30Z |
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| spelling | doaj.art-ce3646603c6b4b5aa3b7f7c2147b9bd72023-11-20T22:46:34ZengMDPI AGMolecules1420-30492020-11-012523560310.3390/molecules25235603Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule InclusionIrina A. Kühne0Kane Esien1Laurence C. Gavin2Helge Müller-Bunz3Solveig Felton4Grace G. Morgan5School of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN, UKSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN, UKSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSpin state preferences for a cationic Mn<sup>3+</sup> chelate complex in four different crystal lattices are investigated by crystallography and SQUID magnetometry. The [MnL<sub>1</sub>]<sup>+</sup> complex cation was prepared by complexation of Mn<sup>3+</sup> 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 [MnL<sub>1</sub>]CF<sub>3</sub>SO<sub>3</sub>·xH<sub>2</sub>O, (<b>1</b>), [MnL<sub>1</sub>]PF<sub>6</sub>·xH<sub>2</sub>O, (<b>2</b>), [MnL<sub>1</sub>]PF<sub>6</sub>·xsal·xH<sub>2</sub>O, (<b>2b</b>), and [MnL<sub>1</sub>]BPh<sub>4</sub>, (<b>3</b>), were dependent on their ability to form strong intermolecular interactions. Complexes (<b>1</b>) and (<b>2</b>), which formed hydrogen bonds between [MnL<sub>1</sub>]<sup>+</sup>, 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 (<b>3</b>) with the BPh<sub>4</sub><sup>−</sup>, counterion and no lattice water, was locked into the high spin state over the same temperature range, as was complex (<b>2b</b>), where inclusion of the 4-methoxysalicylaldehyde guest blocked the H-bonding interaction.https://www.mdpi.com/1420-3049/25/23/5603spin crossoverMn<sup>3+</sup>Schiff basehexadentatesupramolecularguest inclusion |
| spellingShingle | Irina A. Kühne Kane Esien Laurence C. Gavin Helge Müller-Bunz Solveig Felton Grace G. Morgan Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion Molecules spin crossover Mn<sup>3+</sup> Schiff base hexadentate supramolecular guest inclusion |
| title | Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion |
| title_full | Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion |
| title_fullStr | Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion |
| title_full_unstemmed | Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion |
| title_short | Modulation of Mn<sup>3+</sup> Spin State by Guest Molecule Inclusion |
| title_sort | modulation of mn sup 3 sup spin state by guest molecule inclusion |
| topic | spin crossover Mn<sup>3+</sup> Schiff base hexadentate supramolecular guest inclusion |
| url | https://www.mdpi.com/1420-3049/25/23/5603 |
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