Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions
Structural and magnetic properties of a new spin crossover complex [Mn(4,6-diOMe-sal<sub>2</sub>323)]<sup>+</sup> in lattices with ClO<sub>4</sub><sup>−</sup>, (1), NO<sub>3</sub><sup>−</sup>, (2), BF<sub>4</sub><...
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MDPI AG
2022-01-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/8/1/8 |
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| author | Komala Pandurangan Anthony B. Carter Paulo N. Martinho Brendan Gildea Tibebe Lemma Shang Shi Aizuddin Sultan Tia E. Keyes Helge Müller-Bunz Grace G. Morgan |
| author_facet | Komala Pandurangan Anthony B. Carter Paulo N. Martinho Brendan Gildea Tibebe Lemma Shang Shi Aizuddin Sultan Tia E. Keyes Helge Müller-Bunz Grace G. Morgan |
| author_sort | Komala Pandurangan |
| collection | DOAJ |
| description | Structural and magnetic properties of a new spin crossover complex [Mn(4,6-diOMe-sal<sub>2</sub>323)]<sup>+</sup> in lattices with ClO<sub>4</sub><sup>−</sup>, (1), NO<sub>3</sub><sup>−</sup>, (2), BF<sub>4</sub><sup>−</sup>, (3), CF<sub>3</sub>SO<sub>3</sub><sup>−</sup>, (4), and Cl<sup>−</sup> (5) counterions are reported. Comparison with the magnetostructural properties of the C<sub>6</sub>, C<sub>12</sub>, C<sub>18</sub> and C<sub>22</sub> alkylated analogues of the ClO<sub>4</sub><sup>−</sup> salt of [Mn(4,6-diOMe-sal<sub>2</sub>323)]<sup>+</sup> demonstrates that alkylation effectively switches off the thermal spin crossover pathway and the amphiphilic complexes are all high spin. The spin crossover quenching in the amphiphiles is further probed by magnetic, structural and Raman spectroscopic studies of the PF<sub>6</sub><sup>−</sup> salts of the C<sub>6</sub>, C<sub>12</sub> and C<sub>18</sub> complexes of a related complex [Mn(3-OMe-sal<sub>2</sub>323)]<sup>+</sup> which confirm a preference for the high spin state in all cases. Structural analysis is used to rationalize the choice of the spin quintet form in the seven amphiphilic complexes and to highlight the non-accessibility of the smaller spin triplet form of the ion more generally in dilute environments. We suggest that lattice pressure is a requirement to stabilize the spin triplet form of Mn<sup>3+</sup> as the low spin form is not known to exist in solution. |
| first_indexed | 2024-03-10T01:05:32Z |
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| id | doaj.art-8750684d583c490da32b7e04cec66371 |
| institution | Directory Open Access Journal |
| issn | 2312-7481 |
| language | English |
| last_indexed | 2024-03-10T01:05:32Z |
| publishDate | 2022-01-01 |
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| series | Magnetochemistry |
| spelling | doaj.art-8750684d583c490da32b7e04cec663712023-11-23T14:27:09ZengMDPI AGMagnetochemistry2312-74812022-01-0181810.3390/magnetochemistry8010008Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized SolutionsKomala Pandurangan0Anthony B. Carter1Paulo N. Martinho2Brendan Gildea3Tibebe Lemma4Shang Shi5Aizuddin Sultan6Tia E. Keyes7Helge Müller-Bunz8Grace G. Morgan9School of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemical Sciences, Dublin City University, D09 Y5N0 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemical Sciences, Dublin City University, D09 Y5N0 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandSchool of Chemistry, University College Dublin (UCD), Belfield, D04 V1W8 Dublin, IrelandStructural and magnetic properties of a new spin crossover complex [Mn(4,6-diOMe-sal<sub>2</sub>323)]<sup>+</sup> in lattices with ClO<sub>4</sub><sup>−</sup>, (1), NO<sub>3</sub><sup>−</sup>, (2), BF<sub>4</sub><sup>−</sup>, (3), CF<sub>3</sub>SO<sub>3</sub><sup>−</sup>, (4), and Cl<sup>−</sup> (5) counterions are reported. Comparison with the magnetostructural properties of the C<sub>6</sub>, C<sub>12</sub>, C<sub>18</sub> and C<sub>22</sub> alkylated analogues of the ClO<sub>4</sub><sup>−</sup> salt of [Mn(4,6-diOMe-sal<sub>2</sub>323)]<sup>+</sup> demonstrates that alkylation effectively switches off the thermal spin crossover pathway and the amphiphilic complexes are all high spin. The spin crossover quenching in the amphiphiles is further probed by magnetic, structural and Raman spectroscopic studies of the PF<sub>6</sub><sup>−</sup> salts of the C<sub>6</sub>, C<sub>12</sub> and C<sub>18</sub> complexes of a related complex [Mn(3-OMe-sal<sub>2</sub>323)]<sup>+</sup> which confirm a preference for the high spin state in all cases. Structural analysis is used to rationalize the choice of the spin quintet form in the seven amphiphilic complexes and to highlight the non-accessibility of the smaller spin triplet form of the ion more generally in dilute environments. We suggest that lattice pressure is a requirement to stabilize the spin triplet form of Mn<sup>3+</sup> as the low spin form is not known to exist in solution.https://www.mdpi.com/2312-7481/8/1/8spin crossoverSchiff-baseMn<sup>3+</sup>hexadentateJahn–Tellercrystal engineering |
| spellingShingle | Komala Pandurangan Anthony B. Carter Paulo N. Martinho Brendan Gildea Tibebe Lemma Shang Shi Aizuddin Sultan Tia E. Keyes Helge Müller-Bunz Grace G. Morgan Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions Magnetochemistry spin crossover Schiff-base Mn<sup>3+</sup> hexadentate Jahn–Teller crystal engineering |
| title | Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions |
| title_full | Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions |
| title_fullStr | Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions |
| title_full_unstemmed | Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions |
| title_short | Steric Quenching of Mn(III) Thermal Spin Crossover: Dilution of Spin Centers in Immobilized Solutions |
| title_sort | steric quenching of mn iii thermal spin crossover dilution of spin centers in immobilized solutions |
| topic | spin crossover Schiff-base Mn<sup>3+</sup> hexadentate Jahn–Teller crystal engineering |
| url | https://www.mdpi.com/2312-7481/8/1/8 |
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