Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties
Phenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]...
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| Format: | Article |
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MDPI AG
2019-01-01
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| Series: | Crystals |
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| Online Access: | http://www.mdpi.com/2073-4352/9/1/30 |
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| author | Paweł Pakulski Mirosław Arczyński Dawid Pinkowicz |
| author_facet | Paweł Pakulski Mirosław Arczyński Dawid Pinkowicz |
| author_sort | Paweł Pakulski |
| collection | DOAJ |
| description | Phenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]phenanthroline 1,1-dioxide (L), [1,2,5]thiadiazole[3,4-f][4,7]phenanthroline 1,1-dioxide (4,7-L), 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL), and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL) are reported. The preparation of new bromo derivatives of the L: 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL) and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL)—suitable starting materials for further derivatization—are described starting from a commercially available and cheap 1,10-phenanthroline. All PPN salts show antiferromagnetic interactions between the pairs of radical anions, which in the case of PPN(diBrL) are very strong (−116 cm−1; using Ĥ = −2JSS type of exchange coupling Hamiltonian) due to a different crystal packing of the anion radicals as compared to PPN(L), PPN(4,7-L), and PPN(BrL). |
| first_indexed | 2024-04-11T22:35:08Z |
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| id | doaj.art-94169a4a8c9e40e6a426d5a4afb9363d |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-11T22:35:08Z |
| publishDate | 2019-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-94169a4a8c9e40e6a426d5a4afb9363d2022-12-22T03:59:14ZengMDPI AGCrystals2073-43522019-01-01913010.3390/cryst9010030cryst9010030Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic PropertiesPaweł Pakulski0Mirosław Arczyński1Dawid Pinkowicz2Jagiellonian University, Faculty of Chemistry, Gronostajowa 2, 30-387 Kraków, PolandJagiellonian University, Faculty of Chemistry, Gronostajowa 2, 30-387 Kraków, PolandJagiellonian University, Faculty of Chemistry, Gronostajowa 2, 30-387 Kraków, PolandPhenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]phenanthroline 1,1-dioxide (L), [1,2,5]thiadiazole[3,4-f][4,7]phenanthroline 1,1-dioxide (4,7-L), 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL), and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL) are reported. The preparation of new bromo derivatives of the L: 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL) and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL)—suitable starting materials for further derivatization—are described starting from a commercially available and cheap 1,10-phenanthroline. All PPN salts show antiferromagnetic interactions between the pairs of radical anions, which in the case of PPN(diBrL) are very strong (−116 cm−1; using Ĥ = −2JSS type of exchange coupling Hamiltonian) due to a different crystal packing of the anion radicals as compared to PPN(L), PPN(4,7-L), and PPN(BrL).http://www.mdpi.com/2073-4352/9/1/30radical anionredoxmagnetismantiferromagnetic couplingdioxothiadiazole |
| spellingShingle | Paweł Pakulski Mirosław Arczyński Dawid Pinkowicz Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties Crystals radical anion redox magnetism antiferromagnetic coupling dioxothiadiazole |
| title | Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties |
| title_full | Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties |
| title_fullStr | Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties |
| title_full_unstemmed | Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties |
| title_short | Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties |
| title_sort | bis triphenylphosphine iminium salts of dioxothiadiazole radical anions preparation crystal structures and magnetic properties |
| topic | radical anion redox magnetism antiferromagnetic coupling dioxothiadiazole |
| url | http://www.mdpi.com/2073-4352/9/1/30 |
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