Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes
New dinuclear M<sup>II</sup>-Ln<sup>III</sup> complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (Ln<sup>III</sup> = Gd (<b>1</b>), Tb (<b>2...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-02-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/7/2/22 |
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| author | Itziar Oyarzabal Estitxu Echenique-Errandonea Eider San Sebastián Antonio Rodríguez-Diéguez José Manuel Seco Enrique Colacio |
| author_facet | Itziar Oyarzabal Estitxu Echenique-Errandonea Eider San Sebastián Antonio Rodríguez-Diéguez José Manuel Seco Enrique Colacio |
| author_sort | Itziar Oyarzabal |
| collection | DOAJ |
| description | New dinuclear M<sup>II</sup>-Ln<sup>III</sup> complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (Ln<sup>III</sup> = Gd (<b>1</b>), Tb (<b>2</b>), Dy (<b>3</b>) and Er (<b>4</b>)), [Ni(CH<sub>3</sub>CN)(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN (Ln<sup>III</sup> = Nd (<b>5</b>), Gd (<b>6</b>), Tb (<b>7</b>), Dy (<b>8</b>), Er (<b>9</b>) and Y (<b>10</b>)) and [Co(CH<sub>3</sub>CN)(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN (Ln<sup>III</sup> = Gd (<b>11</b>), Tb (<b>12</b>), Dy (<b>13</b>), Er (<b>14</b>) and Y (<b>15</b>)) were prepared from the compartmental ligand <i>N</i>,<i>N</i>′-dimethyl-<i>N</i>,<i>N</i>′-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H<sub>2</sub>L). In all these complexes, the transition metal ions occupy the internal N<sub>2</sub>O<sub>2</sub> coordination site of the ligand, whereas the Ln<sup>III</sup> ions lie in the O<sub>4</sub> external site. Both metallic ions are connected by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged M<sup>II</sup>Ln<sup>III</sup> compounds. Direct current (<i>dc</i>) magnetic measurements allow the study of the magnetic exchange interactions between the 3<i>d</i> and 4<i>f</i> metal ions, which is supported by density functional theory (DFT) theoretical calculations for the Gd<sup>III</sup>-based counterparts. Due to the weak ferromagnetic exchange coupling constants obtained both experimentally and theoretically, the magneto-thermal properties of the less anisotropic systems (compounds <b>1</b> and <b>6</b>) are also studied. Alternating current (<i>ac</i>)magnetic measurements reveal the occurrence of slight frequency dependency of the out-of-phase signal for complexes <b>8</b>, <b>9</b> and <b>13</b>, while complex <b>15</b> displays well-defined maximums below ~6 K. |
| first_indexed | 2024-03-09T05:32:10Z |
| format | Article |
| id | doaj.art-48452632f41148d8a670f7aa49c4ace0 |
| institution | Directory Open Access Journal |
| issn | 2312-7481 |
| language | English |
| last_indexed | 2024-03-09T05:32:10Z |
| publishDate | 2021-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Magnetochemistry |
| spelling | doaj.art-48452632f41148d8a670f7aa49c4ace02023-12-03T12:31:46ZengMDPI AGMagnetochemistry2312-74812021-02-01722210.3390/magnetochemistry7020022Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> ComplexesItziar Oyarzabal0Estitxu Echenique-Errandonea1Eider San Sebastián2Antonio Rodríguez-Diéguez3José Manuel Seco4Enrique Colacio5Departamento de Química Aplicada, Facultad de Química, Universidad del País Vasco UPV/EHU, Paseo Manuel de Lardizabal 3, 20018 Donostia-San Sebastián, SpainDepartamento de Química Aplicada, Facultad de Química, Universidad del País Vasco UPV/EHU, Paseo Manuel de Lardizabal 3, 20018 Donostia-San Sebastián, SpainDepartamento de Química Aplicada, Facultad de Química, Universidad del País Vasco UPV/EHU, Paseo Manuel de Lardizabal 3, 20018 Donostia-San Sebastián, SpainDepartamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, Avda. Fuentenueva S/N, 18002 Granada, SpainDepartamento de Química Aplicada, Facultad de Química, Universidad del País Vasco UPV/EHU, Paseo Manuel de Lardizabal 3, 20018 Donostia-San Sebastián, SpainDepartamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, Avda. Fuentenueva S/N, 18002 Granada, SpainNew dinuclear M<sup>II</sup>-Ln<sup>III</sup> complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN·H<sub>2</sub>O (Ln<sup>III</sup> = Gd (<b>1</b>), Tb (<b>2</b>), Dy (<b>3</b>) and Er (<b>4</b>)), [Ni(CH<sub>3</sub>CN)(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN (Ln<sup>III</sup> = Nd (<b>5</b>), Gd (<b>6</b>), Tb (<b>7</b>), Dy (<b>8</b>), Er (<b>9</b>) and Y (<b>10</b>)) and [Co(CH<sub>3</sub>CN)(µ-L)(µ-OAc)Ln(NO<sub>3</sub>)<sub>2</sub>]·CH<sub>3</sub>CN (Ln<sup>III</sup> = Gd (<b>11</b>), Tb (<b>12</b>), Dy (<b>13</b>), Er (<b>14</b>) and Y (<b>15</b>)) were prepared from the compartmental ligand <i>N</i>,<i>N</i>′-dimethyl-<i>N</i>,<i>N</i>′-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H<sub>2</sub>L). In all these complexes, the transition metal ions occupy the internal N<sub>2</sub>O<sub>2</sub> coordination site of the ligand, whereas the Ln<sup>III</sup> ions lie in the O<sub>4</sub> external site. Both metallic ions are connected by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged M<sup>II</sup>Ln<sup>III</sup> compounds. Direct current (<i>dc</i>) magnetic measurements allow the study of the magnetic exchange interactions between the 3<i>d</i> and 4<i>f</i> metal ions, which is supported by density functional theory (DFT) theoretical calculations for the Gd<sup>III</sup>-based counterparts. Due to the weak ferromagnetic exchange coupling constants obtained both experimentally and theoretically, the magneto-thermal properties of the less anisotropic systems (compounds <b>1</b> and <b>6</b>) are also studied. Alternating current (<i>ac</i>)magnetic measurements reveal the occurrence of slight frequency dependency of the out-of-phase signal for complexes <b>8</b>, <b>9</b> and <b>13</b>, while complex <b>15</b> displays well-defined maximums below ~6 K.https://www.mdpi.com/2312-7481/7/2/22transition metal ionslanthanide(III) metal ionsmolecular magnetismmagneto-caloric effect |
| spellingShingle | Itziar Oyarzabal Estitxu Echenique-Errandonea Eider San Sebastián Antonio Rodríguez-Diéguez José Manuel Seco Enrique Colacio Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes Magnetochemistry transition metal ions lanthanide(III) metal ions molecular magnetism magneto-caloric effect |
| title | Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes |
| title_full | Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes |
| title_fullStr | Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes |
| title_full_unstemmed | Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes |
| title_short | Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3<i>d</i>-4<i>f</i> Complexes |
| title_sort | synthesis structural features and physical properties of a family of triply bridged dinuclear 3 i d i 4 i f i complexes |
| topic | transition metal ions lanthanide(III) metal ions molecular magnetism magneto-caloric effect |
| url | https://www.mdpi.com/2312-7481/7/2/22 |
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