Synthesis and single-molecule magnet properties of a trimetallic dysprosium metallocene cation.

Synthesis and single-molecule magnet properties of a trimetallic dysprosium metallocene cation.
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三金属镝茂金属阳离子的合成及单分子磁体性能

DOI:
10.1039/d1cc02139g
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发表时间:
2021-06-29
期刊:
Chemical communications (Cambridge, England)
影响因子:
--
通讯作者:
Layfield RA
Layfield RA
中科院分区:
其他
文献类型:
--
作者:
He M;Guo FS;Tang J;Mansikkamäki A;Layfield RA

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富瓦烯桥联的二金属镝配合物[{Dy(Cp*)(μ-BH 4)}2(Fvtttt)](1,Cp* = C5 Me 5)转化为三金属硼氢化物桥联的物种[{Dy(Cp*)(Fvtttt)}2Dy(μ-BH 4)3](2)。2与亲电子试剂反应得到[{Dy(Cp*)(μ-BH 4)(Fvtttt)}2Dy][B(C6 F5)4]([3][B(C6 F5)3]),第一个三金属镝阳离子。化合物[3][B(C6 F5)3]也可以通过加入两当量的亲电试剂由1直接形成。一个三倍的增强,从2到3的有效能量势垒的观察和解释与从头计算的帮助。描述了第一个三金属镝单分子磁体。这种材料标志着聚阳离子镝金属茂SMM的性能可能超过领先的系统。
The dimetallic fulvalene-bridged dysprosium complex [{Dy(Cp*)(μ-BH4)}2(Fvtttt)] (1, Cp* = C5Me5) is converted into the trimetallic borohydride-bridged species [{Dy(Cp*)(Fvtttt)}2Dy(μ-BH4)3] (2). In turn, 2 is reacted with a silylium electrophile to give [{Dy(Cp*)(μ-BH4)(Fvtttt)}2Dy][B(C6F5)4] ([3][B(C6F5)3]), the first trimetallic dysprosocenium cation. Compound [3][B(C6F5)3] can also be formed directly from 1 by adding two equivalents of the electrophile. A three-fold enhancement in the effective energy barrier from 2 to 3 is observed and interpreted with the aid of ab initio calculations. The first trimetallic dysprosocenium single-molecule magnet is described. This material signposts a polycationic dysprosium metallocene SMM with properties that could surpass those of leading systems.
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