Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand
Four new compounds of formulas [Cu(hfac)<sub>2</sub>(L)] (<b>1</b>), [Ni(hfac)<sub>2</sub>(L)] (<b>2</b>), [{Cu(hfac)<sub>2</sub>}<sub>2</sub>(µ-L)]·2CH<sub>3</sub>OH (<b>3</b>) and [{Ni(hfac)<sub>2...
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MDPI AG
2021-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/8/2122 |
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| author | Oleh Stetsiuk Abdelkrim El-Ghayoury Francesc Lloret Miguel Julve Narcis Avarvari |
| author_facet | Oleh Stetsiuk Abdelkrim El-Ghayoury Francesc Lloret Miguel Julve Narcis Avarvari |
| author_sort | Oleh Stetsiuk |
| collection | DOAJ |
| description | Four new compounds of formulas [Cu(hfac)<sub>2</sub>(L)] (<b>1</b>), [Ni(hfac)<sub>2</sub>(L)] (<b>2</b>), [{Cu(hfac)<sub>2</sub>}<sub>2</sub>(µ-L)]·2CH<sub>3</sub>OH (<b>3</b>) and [{Ni(hfac)<sub>2</sub>}<sub>2</sub>(µ-L)]·2CH<sub>3</sub>CN (<b>4</b>) [Hhfac = hexafluoroacetylacetone and L = 3,6-bis(picolylamino)-1,2,4,5-tetrazine] have been prepared and their structures determined by X-ray diffraction on single crystals. Compounds <b>1</b> and <b>2</b> are isostructural mononuclear complexes where the metal ions [copper(II) (<b>1</b>) and nickel(II) (<b>2</b>)] are six-coordinated in distorted octahedral MN<sub>2</sub>O<sub>4</sub> surroundings which are built by two bidentate hfac ligands plus another bidentate L molecule. This last ligand coordinates to the metal ions through the nitrogen atoms of the picolylamine fragment. Compounds <b>3</b> and <b>4</b> are centrosymmetric homodinuclear compounds where two bidentate hfac units are the bidentate capping ligands at each metal center and a bis-bidentate L molecule acts as a bridge. The values of the intramolecular metal···metal separation are 7.97 (<b>3</b>) and 7.82 Å (<b>4</b>). Static (dc) magnetic susceptibility measurements were carried out for polycrystalline samples <b>1</b>–<b>4</b> in the temperature range 1.9–300 K. Curie law behaviors were observed for <b>1</b> and <b>2</b>, the downturn of χ<sub>M</sub><i>T</i> in the low temperature region for <b>2</b> being due to the zero-field splitting of the nickel(II) ion. Very weak [<i>J</i> = −0.247(2) cm<sup>−1</sup>] and relatively weak intramolecular antiferromagnetic interactions [<i>J</i> = −4.86(2) cm<sup>−1</sup>] occurred in <b>3</b> and <b>4</b>, respectively (the spin Hamiltonian being defined as <b><i>H</i></b> = −<i>J<b>S</b></i><sub>1</sub>·<b><i>S</i></b><sub>2</sub>). Simple symmetry considerations about the overlap between the magnetic orbitals across the extended bis-bidentate L bridge in <b>3</b> and <b>4</b> account for their magnetic properties. |
| first_indexed | 2024-03-10T12:32:31Z |
| format | Article |
| id | doaj.art-10be3a62d85e4198b5f66d2f20d07465 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T12:32:31Z |
| publishDate | 2021-04-01 |
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| series | Molecules |
| spelling | doaj.art-10be3a62d85e4198b5f66d2f20d074652023-11-21T14:32:47ZengMDPI AGMolecules1420-30492021-04-01268212210.3390/molecules26082122Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine LigandOleh Stetsiuk0Abdelkrim El-Ghayoury1Francesc Lloret2Miguel Julve3Narcis Avarvari4Univ Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, FranceUniv Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, FranceDepartament de Química Inorgànica, Instituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, 46980 Paterna, SpainDepartament de Química Inorgànica, Instituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, 46980 Paterna, SpainUniv Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, FranceFour new compounds of formulas [Cu(hfac)<sub>2</sub>(L)] (<b>1</b>), [Ni(hfac)<sub>2</sub>(L)] (<b>2</b>), [{Cu(hfac)<sub>2</sub>}<sub>2</sub>(µ-L)]·2CH<sub>3</sub>OH (<b>3</b>) and [{Ni(hfac)<sub>2</sub>}<sub>2</sub>(µ-L)]·2CH<sub>3</sub>CN (<b>4</b>) [Hhfac = hexafluoroacetylacetone and L = 3,6-bis(picolylamino)-1,2,4,5-tetrazine] have been prepared and their structures determined by X-ray diffraction on single crystals. Compounds <b>1</b> and <b>2</b> are isostructural mononuclear complexes where the metal ions [copper(II) (<b>1</b>) and nickel(II) (<b>2</b>)] are six-coordinated in distorted octahedral MN<sub>2</sub>O<sub>4</sub> surroundings which are built by two bidentate hfac ligands plus another bidentate L molecule. This last ligand coordinates to the metal ions through the nitrogen atoms of the picolylamine fragment. Compounds <b>3</b> and <b>4</b> are centrosymmetric homodinuclear compounds where two bidentate hfac units are the bidentate capping ligands at each metal center and a bis-bidentate L molecule acts as a bridge. The values of the intramolecular metal···metal separation are 7.97 (<b>3</b>) and 7.82 Å (<b>4</b>). Static (dc) magnetic susceptibility measurements were carried out for polycrystalline samples <b>1</b>–<b>4</b> in the temperature range 1.9–300 K. Curie law behaviors were observed for <b>1</b> and <b>2</b>, the downturn of χ<sub>M</sub><i>T</i> in the low temperature region for <b>2</b> being due to the zero-field splitting of the nickel(II) ion. Very weak [<i>J</i> = −0.247(2) cm<sup>−1</sup>] and relatively weak intramolecular antiferromagnetic interactions [<i>J</i> = −4.86(2) cm<sup>−1</sup>] occurred in <b>3</b> and <b>4</b>, respectively (the spin Hamiltonian being defined as <b><i>H</i></b> = −<i>J<b>S</b></i><sub>1</sub>·<b><i>S</i></b><sub>2</sub>). Simple symmetry considerations about the overlap between the magnetic orbitals across the extended bis-bidentate L bridge in <b>3</b> and <b>4</b> account for their magnetic properties.https://www.mdpi.com/1420-3049/26/8/21221,2,4,5-tetrazinenitrogen ligandsnickelcoppercrystal structure determinationmagnetic properties |
| spellingShingle | Oleh Stetsiuk Abdelkrim El-Ghayoury Francesc Lloret Miguel Julve Narcis Avarvari Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand Molecules 1,2,4,5-tetrazine nitrogen ligands nickel copper crystal structure determination magnetic properties |
| title | Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand |
| title_full | Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand |
| title_fullStr | Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand |
| title_full_unstemmed | Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand |
| title_short | Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand |
| title_sort | mono and binuclear copper ii and nickel ii complexes with the 3 6 bis picolylamino 1 2 4 5 tetrazine ligand |
| topic | 1,2,4,5-tetrazine nitrogen ligands nickel copper crystal structure determination magnetic properties |
| url | https://www.mdpi.com/1420-3049/26/8/2122 |
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