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Synthesis and magneto-structural studies on a new family of carbonato bridged 3d–4f complexes featuring a [CoII3LnIII3(CO3)] (Ln = La, Gd, Tb, Dy and Ho) core: slow magnetic relaxation displayed by the cobalt(ii)–dysprosium(iii) analogue
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 3/14/2018, Vol. 47 Issue 10, p3425-3439, 15p
- Publication Year :
- 2018
-
Abstract
- A new family of [3 + 3] hexanuclear 3d–4f complexes [(μ<subscript>3</subscript>-CO<subscript>3</subscript>){Co<superscript>II</superscript>Ln<superscript>III</superscript>L(μ<subscript>3</subscript>-OH)(OH<subscript>2</subscript>)}<subscript>3</subscript>]-(ClO<subscript>4</subscript>)·mC<subscript>2</subscript>H<subscript>5</subscript>OH·nH<subscript>2</subscript>O (1–5) [Ln = La (1), Gd (2), Tb (3), Dy (4), and Ho (5)] have been prepared in moderate to high yields (62–78%) following a self-assembly reaction between the ligand 6,6′,6′′-(nitrilotris(methylene))tris-(2-methoxy-4-methylphenol) (H<subscript>3</subscript>L), Co(OAc)<subscript>2</subscript>·4H<subscript>2</subscript>O and the lanthanide ion precursors in the mandatory presence of tetrabutylammonium hydroxide. During the reaction, atmospheric carbon dioxide is fixed in the product molecule as a bridging carbonato ligand which connects all the three lanthanide centers of this molecular assembly through a rare η<superscript>2</superscript>:η<superscript>2</superscript>:η<superscript>2</superscript>–μ<subscript>3</subscript> mode of bridging as revealed from X-ray crystallography. The metal centers in all these compounds, except the Gd<superscript>III</superscript> analogue (2), are coupled in antiferromagnetic manner while the nature of coupling in the CoII3GdIII3 complex is ferromagnetic. DFT calculations revealed that this ferromagnetic interaction occurs most likely by the Co<superscript>II</superscript>–Gd<superscript>III</superscript> superexchange, mediated via the bridging oxygen atoms. Only the Co<superscript>II</superscript>–Dy<superscript>III</superscript> compound (4) displayed a slow relaxation of the magnetization at a very low temperature as established by AC susceptibility measurements. The data provides an estimation of the activation energy U/k<subscript>B</subscript> = 9.2 K and the relaxation time constant τ<subscript>0</subscript> = 1.0 × 10<superscript>−7</superscript> s. [ABSTRACT FROM AUTHOR]
- Subjects :
- COMPLEX compounds synthesis
METAL complexes
MAGNETIC relaxation
Subjects
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 47
- Issue :
- 10
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 128324418
- Full Text :
- https://doi.org/10.1039/c7dt04389a