Placing a crown on Dy super(III) - a dual property Ln super(III) crown ether complex displaying optical properties and SMM behaviour

Two mononuclear Dy super(III) crown ether complexes [Dy(15C5)(H sub(2)O) sub(4)](ClO sub(4)) sub(3).(15C5).H sub(2)O (1) and [Dy(12C4)(H sub(2)O) sub(5)](ClO sub(4)) sub(3).H sub(2)O (2) have been prepared and characterized. X-ray diffraction studies show that both compounds crystallize as half sand...

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Bibliographic Details
Published in:Journal of materials chemistry. C, Materials for optical and electronic devices Materials for optical and electronic devices, 2015-07, Vol.3 (29), p.7738-7747
Main Authors: Gavey, Emma L, Al Hareri, Majeda, Regier, Jeffery, Carlos, Luis D, Ferreira, Rute AS, Razavi, Fereidoon S, Rawson, Jeremy M, Pilkington, Melanie
Format: Article
Language:English
Subjects:
Crown ethers
Diffraction
Fine structure
Ground state
Grounds
Magnetic properties
Mathematical analysis
Splitting
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Summary:Two mononuclear Dy super(III) crown ether complexes [Dy(15C5)(H sub(2)O) sub(4)](ClO sub(4)) sub(3).(15C5).H sub(2)O (1) and [Dy(12C4)(H sub(2)O) sub(5)](ClO sub(4)) sub(3).H sub(2)O (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 super(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 super(4)F sub(9/2) arrow right super(6)H sub(15/2) band, the Stark splitting of the super(6)H sub(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 plus or minus 3.0 cm super(-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 plus or minus 3.0 cm super(-1)) in which a rapid relaxation process affords no SMM behaviour in zero-field.
ISSN:2050-7526
2050-7534
DOI:10.1039/c5tc01264c