Baldoví José J, Duan Yan, Bustos Carlos, Cardona-Serra Salvador, Gouzerh Pierre, Villanneau Richard, Gontard Geoffrey, Clemente-Juan Juan M, Gaita-Ariño Alejandro, Giménez-Saiz Carlos, Proust Anna, Coronado Eugenio
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltran, 2, E-46980 Paterna, Spain.
Facultad de Ciencia, Instituto de Química, Campus Isla Teja, Universidad Austral de Chile, Valdivia, Chile and Sorbonne Universites, UPMC-Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, F-75005 Paris, France.
Dalton Trans. 2016 Oct 25;45(42):16653-16660. doi: 10.1039/c6dt02258h.
Polyoxometalate (POM) chemistry has recently offered excellent examples of single ion magnets (SIMs) and molecular spin qubits. Compared with conventional coordination compounds, POMs provide rigid and highly symmetric coordination sites. However, all POM-based SIMs reported to date exhibit a very limited range of possibilities for chemical processability. We present herein two new families of POM-based SIMs which are soluble in organic solvents: [Ln(β-MoO)] {Ln = Tb, Dy, Ho, Er, Tm and Yb} and the functionalised POMs [Ln{MoO(OMe)NNCH-p-NO}] {Ln = Tb, Dy, Ho, Er, Yb and Nd}. In addition, these two families represent the first SIMs based on polyoxomolybdates. A magneto-structural analysis of these families is presented, which is based on an effective crystal field model, and compared with the results reported in analogous lanthanoid SIMs based on polyoxotungstates.
多金属氧酸盐(POM)化学最近为单离子磁体(SIMs)和分子自旋量子比特提供了出色的实例。与传统配位化合物相比,POM提供了刚性且高度对称的配位位点。然而,迄今为止报道的所有基于POM的SIMs在化学可加工性方面的可能性范围非常有限。我们在此展示了两类可溶于有机溶剂的基于POM的新SIMs:[Ln(β-MoO)] {Ln = 铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)和镱(Yb)} 以及功能化的POMs [Ln{MoO(OMe)NNCH-p-NO}] {Ln = 铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、镱(Yb)和钕(Nd)}。此外,这两类是首批基于多钼酸盐的SIMs。本文基于有效晶体场模型对这两类进行了磁结构分析,并与基于多钨酸盐的类似镧系SIMs所报道的结果进行了比较。