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Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit
The new heterometallic compounds, [{Cu(pn)(2)}(2)Ni(NCS)(6)](n)·2nH(2)O (1), [{Cu(II)(trien)}(2)Ni(NCS)(6)Cu(I)(NCS)](n) (2) and [Cu(tren)(NCS)](4)[Ni(NCS)(6)] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray an...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9861906/ https://www.ncbi.nlm.nih.gov/pubmed/36676467 http://dx.doi.org/10.3390/ma16020731 |
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author | Tereba, Natalia Muzioł, Tadeusz M. Wiśniewska, Joanna Podgajny, Robert Bieńko, Alina Wrzeszcz, Grzegorz |
author_facet | Tereba, Natalia Muzioł, Tadeusz M. Wiśniewska, Joanna Podgajny, Robert Bieńko, Alina Wrzeszcz, Grzegorz |
author_sort | Tereba, Natalia |
collection | PubMed |
description | The new heterometallic compounds, [{Cu(pn)(2)}(2)Ni(NCS)(6)](n)·2nH(2)O (1), [{Cu(II)(trien)}(2)Ni(NCS)(6)Cu(I)(NCS)](n) (2) and [Cu(tren)(NCS)](4)[Ni(NCS)(6)] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [Cu(II)(tren)](2+) antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {Ni(II)Cu(II)(2)} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)(3)](3−) linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 → 2 → 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment. |
format | Online Article Text |
id | pubmed-9861906 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-98619062023-01-22 Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit Tereba, Natalia Muzioł, Tadeusz M. Wiśniewska, Joanna Podgajny, Robert Bieńko, Alina Wrzeszcz, Grzegorz Materials (Basel) Article The new heterometallic compounds, [{Cu(pn)(2)}(2)Ni(NCS)(6)](n)·2nH(2)O (1), [{Cu(II)(trien)}(2)Ni(NCS)(6)Cu(I)(NCS)](n) (2) and [Cu(tren)(NCS)](4)[Ni(NCS)(6)] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [Cu(II)(tren)](2+) antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {Ni(II)Cu(II)(2)} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)(3)](3−) linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 → 2 → 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment. MDPI 2023-01-11 /pmc/articles/PMC9861906/ /pubmed/36676467 http://dx.doi.org/10.3390/ma16020731 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Tereba, Natalia Muzioł, Tadeusz M. Wiśniewska, Joanna Podgajny, Robert Bieńko, Alina Wrzeszcz, Grzegorz Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title | Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title_full | Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title_fullStr | Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title_full_unstemmed | Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title_short | Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)(6)](4−) Unit |
title_sort | structural diversity, xas and magnetism of copper(ii)-nickel(ii) heterometallic complexes based on the [ni(ncs)(6)](4−) unit |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9861906/ https://www.ncbi.nlm.nih.gov/pubmed/36676467 http://dx.doi.org/10.3390/ma16020731 |
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