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Issue 4, 2020
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Slow magnetic relaxation in CoII–LnIII heterodinuclear complexes achieved through a functionalized nitronyl nitroxide biradical

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Abstract

A new nitronyl nitroxide biradical ligand NITPh-PyPzbis (5-(3-(2-pyridinyl)-1H-pyrazol-1-yl)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene) has been successfully applied for constructing a 3d–4f CoII–LnIII system, giving rise to a family of novel hetero-tri-spin complexes, namely, [LnCo(hfac)5(NITPh-PyPzbis)]·CH2Cl2 (LnCo = YCo 1, GdCo 2, TbCo 3, DyCo 4, and HoCo 5; hfac = hexafluoroacetylacetonate). In these hetero-tri-spin complexes, the NITPh-PyPzbis biradical chelates one LnIII and one CoII simultaneously by means of its adjacent aminoxyl moieties and two N donors from the 3-(2-pyridinyl)-1H-pyrazol-1-yl unit, respectively, realizing the unique biradical-Co–Ln heterodinuclear structure. Direct-current magnetic susceptibility investigations show that antiferromagnetic coupling is predominant in the YCo derivative, while the leading magnetic interaction in the GdCo analogue is ferromagnetic. Alternating-current data for the DyCo complex display visible temperature/frequency-dependent χ′′ peaks, indicating the SMM behavior. In the fluorescence spectra, four characteristic emission bands of the TbIII ion have been detected for the TbCo analogue.

Graphical abstract: Slow magnetic relaxation in CoII–LnIII heterodinuclear complexes achieved through a functionalized nitronyl nitroxide biradical

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Article information


Submitted
15 Oct 2019
Accepted
12 Dec 2019
First published
13 Dec 2019

Dalton Trans., 2020,49, 1089-1096
Article type
Paper

Slow magnetic relaxation in CoII–LnIII heterodinuclear complexes achieved through a functionalized nitronyl nitroxide biradical

L. Xi, J. Sun, K. Wang, J. Lu, P. Jing and L. Li, Dalton Trans., 2020, 49, 1089
DOI: 10.1039/C9DT04036F

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