Placing a crown on Dy-III - a dual property Ln(III) crown ether complex displaying optical properties and SMM behaviour
Two mononuclear Dy-III crown ether complexes [Dy(15C5)(H2O)(4)](ClO4)(3)center dot(15C5)center dot H2O (1) and [Dy(12C4)(H2O)(5)](ClO4)(3)center dot H2O (2) have been prepared and characterized. X-ray diffraction studies show that both compounds crystallize as half sandwich type structures with muff...
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| Outros Autores: | , , , , , , |
| Formato: | article |
| Idioma: | eng |
| Publicado em: |
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| Assuntos: | |
| Texto completo: | http://hdl.handle.net/10773/19646 |
| País: | Portugal |
| Oai: | oai:ria.ua.pt:10773/19646 |
| Resumo: | Two mononuclear Dy-III crown ether complexes [Dy(15C5)(H2O)(4)](ClO4)(3)center dot(15C5)center dot H2O (1) and [Dy(12C4)(H2O)(5)](ClO4)(3)center dot H2O (2) have been prepared and characterized. X-ray diffraction studies show that both compounds crystallize as half sandwich type structures with muffin and pseudo-capped square antiprismatic geometries respectively. Despite the comparable local environments of the Dy-III ions they display remarkably different dynamic magnetic properties with only 1 displaying SMM properties in zero field. The solid state emission spectra for both 1 and 2 display sharp bands associated with f-f transitions. From the fine structure of the F-4(9/2) -> H-6(15/2) band, the Stark splitting of the H-6(15/2) ground state permitted the energy difference between the ground and first excited state to be determined. For 1 this value (Delta E = 58.0 +/- 3.0 cm(-1) ) is in excellent agreement with ab initio calculations and the experimentally observed SMM behaviour. For 2, the photoluminescence data and theoretical calculations support a less well isolated ground state (Delta E = 30 +/- 3.0 cm(-1)) in which a rapid relaxation process affords no SMM behaviour in zero-field. |
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