TY - JOUR
T1 - Construction of a general library for the rational design of nanomagnets and spin qubits based on mononuclear f.block complexes. The polyoxometalate case
AU - Baldoví, José J.
AU - Clemente-Juan, Juan M.
AU - Coronado, Eugenio
AU - Duan, Yan
AU - Gaita-Ariño, Alejandro
AU - Giménez-Saiz, Carlos
N1 - Publisher Copyright:
© 2014 American Chemical Society.
PY - 2014/9/15
Y1 - 2014/9/15
N2 - This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2]9-. and [Ln(β2-SiW11O39)2]13-. (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associated wave functions of the studied systems, which is fully consistent with the observed magnetic behavior. In order to demonstrate the predictive character of this model, we have extended our model in a first step to calculate the properties of the POM complexes of the early 4f-block metals. In doing so, [Nd(W5O18)2]9-. has been identified as a suitable candidate to exhibit SMM behavior. Magnetic experiments have confirmed such a prediction, demonstrating the usefulness of this strategy for the directed synthesis of new nanomagnets. Thus, with an effective barrier of 51.4 cm-1 under an applied dc field of 1000 Oe, this is the second example of a Nd3+-based single-ion magnet.
AB - This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2]9-. and [Ln(β2-SiW11O39)2]13-. (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associated wave functions of the studied systems, which is fully consistent with the observed magnetic behavior. In order to demonstrate the predictive character of this model, we have extended our model in a first step to calculate the properties of the POM complexes of the early 4f-block metals. In doing so, [Nd(W5O18)2]9-. has been identified as a suitable candidate to exhibit SMM behavior. Magnetic experiments have confirmed such a prediction, demonstrating the usefulness of this strategy for the directed synthesis of new nanomagnets. Thus, with an effective barrier of 51.4 cm-1 under an applied dc field of 1000 Oe, this is the second example of a Nd3+-based single-ion magnet.
UR - http://www.scopus.com/inward/record.url?scp=84919752645&partnerID=8YFLogxK
U2 - 10.1021/ic501867d
DO - 10.1021/ic501867d
M3 - Article
AN - SCOPUS:84919752645
SN - 0020-1669
VL - 53
SP - 9976
EP - 9980
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -