Modulated spin dynamics of [Co₂] coordination helicates <i>via</i> differential strand composition

Barrios, Leoní A. ; Capó, Nuria ; Boulehjour, Hanae ; Reta, Daniel ; Tejedor, Inés (Universidad de Zaragoza) ; Roubeau, Olivier ; Aromí, Guillem

Resumen: Coordination supramolecular chemistry provides a versatile entry into materials with functionalities of technological relevance at the nanoscale. Here, we describe how two different bis-pyrazolylpyridine ligands (L1 and L2) assemble with Co(II) ions into dinuclear triple-stranded helicates, in turn, encapsulating different anionic guests. These constructs are described as (Cl@[Co2(L1)3])3+, (SiF6@[Co2(L1)(L2)3])2+ and (ClO4@[Co2(L2)3])3+, as established by single-crystal X-ray diffraction. Extensive magnetic and calorimetric measurements, numerical treatments and theoretical calculations reveal that the individual Co(II) centers of these supramolecular entities exhibit field-induced slow relaxation of magnetization, dominated by direct and Raman mechanisms. While the small variations in the spin dynamics are not easily correlated with the evident structural differences among the three species, the specific heat measurements suggest two vibronic pathways of magnetic relaxation: one that would be associated with the host lattice and another linked with the guest.

Idioma: Inglés

DOI: 10.1039/d4dt00629a

Año: 2024

Publicado en: Dalton Transactions 53, 17 (2024), 7611-7618
ISSN: 1477-9226

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2020-118329RB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137764OB-I00
Financiación: info:eu-repo/grantAgreement/EUR/MICINN/TED2021-129214B-I00

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Física (Dpto. Química Física)