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Lanthanoid pyridyl-β-diketonate 'triangles'. New examples of single molecule toroics

Caporale, C, Sobolev, AN, Phonsri, W, Murray, KS, Swain, A, Rajaraman, G, Ogden, MI, Massi, M and Fuller, RO ORCID: 0000-0003-3926-8680 2020 , 'Lanthanoid pyridyl-β-diketonate 'triangles'. New examples of single molecule toroics' , Dalton Transactions, vol. 49, no. 47 , pp. 17421-17432 , doi: 10.1039/d0dt02855j.

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Abstract

Trinuclear lanthanoid clusters have been synthesised and investigated as toroidal spin systems. A pyridyl functionalised β-diketonate, 1,3-bis(pyridin-2-yl)propane-1,3-dione (o-dppdH) has been used to synthesise a family of clusters of the form [Dy3(OH)2(o-dppd)3Cl2(H2O)4]Cl2·7H2O (1), [Tb3(o-dppd)3(μ3-OH)2(CH3CH2OH)3Cl3][Tb3(o-dppd)3(μ3-OH)2(H2O)(CH3CH2OH)2Cl3]Cl2·H2O (2), [Ho3(OH)2(o-dppd)3Cl(H2O)5]Cl3·3H2O (3) and [Er3(OH)2(o-dppd)3Cl2(H2O)3(CH3OH)]Cl2·3H2O·CH3OH (4). Despite the previous occurrence of this structural motif in the literature, these systems have not been widely investigated in terms of torodic behaviour. Magnetic studies were used to further characterise the complexes. DC susceptibility studies support weak antiferromagnetic exchange in the complexes. Slow magnetic relaxation behaviour is observed in the dynamic AC magnetic studies for complex 1. Theoretical studies predict that complex 1 and 3 have a non-magnetic ground state based on a toroidal arrangement of spins. Changes to the coordination environment in 2 do not support a toroic spin state. The prolate nature of the ErIII centres in complex 4 and large transverse anisotropy do not support the toroidal arrangement of lanthanoid spins in the complex.

Item Type: Article
Authors/Creators:Caporale, C and Sobolev, AN and Phonsri, W and Murray, KS and Swain, A and Rajaraman, G and Ogden, MI and Massi, M and Fuller, RO
Keywords: lanthanoid, toroidal spin, magnetism
Journal or Publication Title: Dalton Transactions
Publisher: Royal Soc Chemistry
ISSN: 1477-9226
DOI / ID Number: 10.1039/d0dt02855j
Copyright Information:

Copyright 2020 The Royal Society of Chemistry

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