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Pentanuclear [2.2] spirocyclic lanthanide(III) complexes: slow magnetic relaxation of the Dy-III analogue
- Pentanuclear [2.2] spirocyclic lanthanide(III) complexes: slow magnetic relaxation of the Dy-III analogue
- Biswas, Sourav; Das, Sourav; van Leusen, Jan; Koegerler, Paul; Chandrasekhar, Vadapalli
- DGIST Authors
- Das, Sourav
- Issue Date
- Dalton Transactions, 44(44), 19282-19293
- Article Type
- Alternating Current; Antiferromagnetic Exchange Interactions; Chemical Analysis; Chlorine Compounds; Coordinating Ligands; Dysprosium; Electric Impedance Measurement; Lanthanide Complex; Ligands; Low Temperatures; Magnetic Susceptibility; Magnetic Susceptibility Measurements; Pentanuclear Complexes; Relaxation Processes; Slow Magnetic Relaxations; Temperature
- The reaction of LnCl3·6H2O (Ln = Dy3+, Tb3+ and Ho3+) with the multisite coordinating ligand N′-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylidene)acetohydrazide (LH3) in the presence of pivalic acid (PivH) leads to the formation of three isostructural homometallic pentanuclear complexes, [Dy5(LH)4(η1-Piv)(η2-Piv)3(μ2-η2η1Piv)2(H2O)]·Cl·9·5H2O·5MeOH (1), [Tb5(LH)4(η1-Piv)(η2-Piv)3(μ2-η2η1Piv)2(H2O)]·Cl·10.5H2O·2MeOH·2CHCl3 (2) and [Ho5(LH)4(η1-Piv)(η2-Piv)3(μ2-η2η1Piv)2(H2O)]·Cl·14.5H2O·2CHCl3 (3). 1-3 are monocationic and are comprised of four doubly deprotonated [LH]2- ligands along with six pivalate ions. These complexes possess a [2.2] spirocyclic topology formed by the fusion of two triangles of LnIII ions at a common vertex. The magneto chemical analysis reveals the presence of antiferromagnetic exchange interactions at low temperature, and the DyIII complex 1 gives an out-of-phase signal with a small curvature in alternating current (ac) magnetic susceptibility measurement. Application of a 3000 G static field during ac measurement intensifies the signals, revealing a second slow relaxation process in the DyIII analogue. © The Royal Society of Chemistry.
- Royal Society of Chemistry
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