Tetrametallic Ln(III) (Ln = Gd, Dy) phosphonate clusters: Spin cooler and single-molecule magnet

Tetrametallic Ln(III) (Ln = Gd, Dy) phosphonate clusters: Spin cooler and single-molecule magnet
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DOI:
10.1016/j.ica.2018.07.040
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发表时间:
2018-10
影响因子:
2.8
通讯作者:
Xiaoyan Tang;Jingkun Hua;Yunsheng Ma;A. Hori;R. Yuan;R. Matsuda
Xiaoyan Tang;Jingkun Hua;Yunsheng Ma;A. Hori;R. Yuan;R. Matsuda
中科院分区:
化学3区
文献类型:
--
作者:
Xiaoyan Tang;Jingkun Hua;Yunsheng Ma;A. Hori;R. Yuan;R. Matsuda

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本文报道了从双核镧系元素前体[Ln 2(O2 CtBu)6(HO 2 CtBu)6]和大体积膦酸配体(9-甲基-9H-芴-9-基)膦酸(RPO 3 H 2)中方便地获得四核簇合物[Ln 4(RPO 3)2(RPO 3 H)(tBuCO 2)7(tBuCO 2 H)3(H2 O)3]·solventLn 4(Ln = Gd,Dy)。在Ln 4的结构中,四个Ln(III)离子排列在被庞大的疏水芴基包裹的不规则四边形的顶点处。磁性研究表明,Gd 4表现出高磁热效应(MCE),在2.5 K(ΔH= 7 T)下熵变为23.10 J kg− 1 K − 1,而Dy 4表现出慢磁弛豫,这是单分子磁体(SMM)的特征。
We report herein convenient access to tetranuclear clusters of [Ln4(RPO3)2(RPO3H)(tBuCO2)7(tBuCO2H)3(H2O)3]·solventLn4(Ln = Gd, Dy), from dinuclear lanthanide precursors [Ln2(O2CtBu)6(HO2CtBu)6] and a bulky phosphonate ligand (9-methyl-9H-fluoren-9-yl)phosphonic acid (RPO3H2). In the structures ofLn4, four Ln(III) ions are arranged at the vertices of an irregular quadrilateral that are wrapped by bulky hydrophobic fluorenyl groups. Magnetic studies show thatGd4exhibits high magnetocaloric effect (MCE) with entropy change of 23.10 J kg−1K−1at 2.5 K forΔH= 7 T, whileDy4shows slow magnetic relaxation that is the character of a single-molecule magnet (SMM).