Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand
A new asymmetrically substituted ONOO Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (<b>nanc</b>H<sub>2</sub>) was prepared from the condensation of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid. <b>nanc</b>H<sub>2<...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-01-01
|
| Series: | Chemistry |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2624-8549/5/1/7 |
| _version_ | 1797612886012461056 |
|---|---|
| author | Anne Worrell Gabriele Delle Monache Mark M. Turnbull Jeremy M. Rawson Theocharis C. Stamatatos Melanie Pilkington |
| author_facet | Anne Worrell Gabriele Delle Monache Mark M. Turnbull Jeremy M. Rawson Theocharis C. Stamatatos Melanie Pilkington |
| author_sort | Anne Worrell |
| collection | DOAJ |
| description | A new asymmetrically substituted ONOO Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (<b>nanc</b>H<sub>2</sub>) was prepared from the condensation of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid. <b>nanc</b>H<sub>2</sub> reacts with Cu<sub>2</sub>(O<sub>2</sub>CMe)<sub>4</sub>·2H<sub>2</sub>O in the presence of Gd(O<sub>2</sub>CMe)<sub>3</sub>·6H<sub>2</sub>O to afford a uniform one-dimensional homometallic chain, [Cu<sup>II</sup>(<b>nanc</b>)]<i><sub>n</sub></i> (<b>1</b>). The structure of <b>1</b> was elucidated via single crystal X-ray diffraction studies, which revealed that the Cu(II) ions adopt distorted square planar geometries and are coordinated in a tridentate manner by an [ONO] donor set from one <b>nanc</b><sup>2−</sup> ligand and an O<sup>−</sup> of a bridging carboxylate group from a second ligand. The bridging carboxylato group of the <b>nanc</b><sup>2−</sup> ligand adopts a syn, anti-η<sup>1</sup>:η<sup>1</sup>:μ conformation linking neighboring Cu(II) ions, forming a 1D chain. The magnetic susceptibility of <b>1</b> follows Curie–Weiss law in the range 45–300 K (C = 0.474(1) emu K mol-1, <i>θ</i> = +7.9(3) K), consistent with ferromagnetic interactions between <i>S</i> = ½ Cu(II) ions with g = 2.248. Subsequently, the data fit well to the 1D quantum Heisenberg ferromagnetic (QHFM) chain model with g = 2.271, and <i>J</i> = +12.3 K. DFT calculations, implementing the broken symmetry approach, were also carried out on a model dimeric unit extracted from the polymeric chain structure. The calculated exchange coupling via the carboxylate bridge (<i>J</i> = +13.8 K) is consistent with the observed ferromagnetic exchange between neighbouring Cu(II) centres. |
| first_indexed | 2024-03-11T06:47:12Z |
| format | Article |
| id | doaj.art-f3d2ce7a47fd47bdbb94b3326d13157b |
| institution | Directory Open Access Journal |
| issn | 2624-8549 |
| language | English |
| last_indexed | 2024-03-11T06:47:12Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Chemistry |
| spelling | doaj.art-f3d2ce7a47fd47bdbb94b3326d13157b2023-11-17T10:15:25ZengMDPI AGChemistry2624-85492023-01-0151859610.3390/chemistry5010007Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base LigandAnne Worrell0Gabriele Delle Monache1Mark M. Turnbull2Jeremy M. Rawson3Theocharis C. Stamatatos4Melanie Pilkington5Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, CanadaDepartment of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, CanadaCarlson School of Chemistry and Biochemistry, Clark University, 950 Main St., Worcester, MA 01610, USADepartment of Chemistry and Biochemistry, University of Windsor, 401 Sunset Ave, Windsor, ON N9B 3P4, CanadaDepartment of Chemistry, University of Patras, 26504 Patras, GreeceDepartment of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, CanadaA new asymmetrically substituted ONOO Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (<b>nanc</b>H<sub>2</sub>) was prepared from the condensation of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid. <b>nanc</b>H<sub>2</sub> reacts with Cu<sub>2</sub>(O<sub>2</sub>CMe)<sub>4</sub>·2H<sub>2</sub>O in the presence of Gd(O<sub>2</sub>CMe)<sub>3</sub>·6H<sub>2</sub>O to afford a uniform one-dimensional homometallic chain, [Cu<sup>II</sup>(<b>nanc</b>)]<i><sub>n</sub></i> (<b>1</b>). The structure of <b>1</b> was elucidated via single crystal X-ray diffraction studies, which revealed that the Cu(II) ions adopt distorted square planar geometries and are coordinated in a tridentate manner by an [ONO] donor set from one <b>nanc</b><sup>2−</sup> ligand and an O<sup>−</sup> of a bridging carboxylate group from a second ligand. The bridging carboxylato group of the <b>nanc</b><sup>2−</sup> ligand adopts a syn, anti-η<sup>1</sup>:η<sup>1</sup>:μ conformation linking neighboring Cu(II) ions, forming a 1D chain. The magnetic susceptibility of <b>1</b> follows Curie–Weiss law in the range 45–300 K (C = 0.474(1) emu K mol-1, <i>θ</i> = +7.9(3) K), consistent with ferromagnetic interactions between <i>S</i> = ½ Cu(II) ions with g = 2.248. Subsequently, the data fit well to the 1D quantum Heisenberg ferromagnetic (QHFM) chain model with g = 2.271, and <i>J</i> = +12.3 K. DFT calculations, implementing the broken symmetry approach, were also carried out on a model dimeric unit extracted from the polymeric chain structure. The calculated exchange coupling via the carboxylate bridge (<i>J</i> = +13.8 K) is consistent with the observed ferromagnetic exchange between neighbouring Cu(II) centres.https://www.mdpi.com/2624-8549/5/1/7Cu(II)Schiff basearomatic ligandsferromagnetic interactionsone-dimensional uniform chaincoordination polymer |
| spellingShingle | Anne Worrell Gabriele Delle Monache Mark M. Turnbull Jeremy M. Rawson Theocharis C. Stamatatos Melanie Pilkington Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand Chemistry Cu(II) Schiff base aromatic ligands ferromagnetic interactions one-dimensional uniform chain coordination polymer |
| title | Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand |
| title_full | Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand |
| title_fullStr | Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand |
| title_full_unstemmed | Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand |
| title_short | Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand |
| title_sort | synthesis structural magnetic and computational studies of a one dimensional ferromagnetic cu ii chain assembled from a new schiff base ligand |
| topic | Cu(II) Schiff base aromatic ligands ferromagnetic interactions one-dimensional uniform chain coordination polymer |
| url | https://www.mdpi.com/2624-8549/5/1/7 |
| work_keys_str_mv | AT anneworrell synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand AT gabrieledellemonache synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand AT markmturnbull synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand AT jeremymrawson synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand AT theochariscstamatatos synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand AT melaniepilkington synthesisstructuralmagneticandcomputationalstudiesofaonedimensionalferromagneticcuiichainassembledfromanewschiffbaseligand |