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

ABSTRACT: 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.

SUBMITTER: He M

PROVIDER: S-EPMC8240697 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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

He Mian M Guo Fu-Sheng FS Tang Jinkui J Mansikkamäki Akseli A Layfield Richard A RA

Chemical communications (Cambridge, England) 20210601 52

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 effecti ...[more]

PMID: 34085074

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Project description:Treatment of the new methanediide-methanide complex [Dy(SCS)(SCSH)(THF)] (1Dy, SCS = {C(PPh2S)2}2-) with alkali metal alkyls and auxillary ethers produces the bis-methanediide complexes [Dy(SCS)2][Dy(SCS)2(K(DME)2)2] (2Dy), [Dy(SCS)2][Na(DME)3] (3Dy) and [Dy(SCS)2][K(2,2,2-cryptand)] (4Dy). For further comparisons, the bis-methanediide complex [Dy(NCN)2][K(DB18C6)(THF)(toluene)] (5Dy, NCN = {C(PPh2NSiMe3)2}2-, DB18C6 = dibenzo-18-crown-6 ether) was prepared. Magnetic susceptibility experiments reveal slow relaxation of the magnetisation for 2Dy-5Dy, with open magnetic hysteresis up to 14, 12, 15, and 12 K, respectively (∼14 Oe s-1). Fitting the alternating current magnetic susceptibility data for 2Dy-5Dy gives energy barriers to magnetic relaxation (U eff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy-4Dy join a privileged group of SMMs with U eff values of ∼1000 K and greater with magnetic hysteresis at temperatures >10 K. These structurally similar Dy-components permit systematic correlation of the effects of axial and equatorial ligand fields on single-molecule magnet performance. For 2Dy-4Dy, the Dy-components can be grouped into 2Dy-cation/4Dy and 2Dy-anion/3Dy, where the former have almost linear C[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with short average Dy[double bond, length as m-dash]C distances, and the latter have more bent C[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with longer average Dy[double bond, length as m-dash]C bonds. Both U eff and hysteresis temperature are superior for the former pair compared to the latter pair as predicted, supporting the hypothesis that a more linear axial ligand field with shorter M-L distances produces enhanced SMM properties. Comparison with 5Dy demonstrates unusually clear-cut examples of: (i) weakening the equatorial ligand field results in enhancement of the SMM performance of a monometallic system; (ii) a positive correlation between U eff barrier and axial linearity in structurally comparable systems.

Dataset Information

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

Publications

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

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