Synthesis and single-molecule magnet properties of a trimetallic dysprosium metallocene cation. Issue 52 (4th June 2021)

• Record Type: Journal Article
• Authors: He, Mian; Guo, Fu-Sheng; Tang, Jinkui; Mansikkamäki, Akseli; Layfield, Richard A.
• Is Part Of: Chemical communications. Volume 57:Issue 52(2021)
• Page Start: 6396
• Page End: 6399
• Publication Date: 2021-06-04
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/d1cc02139g
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : 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. Abstract : The dimetallic fulvalene-bridged dysprosium complex [{Dy(Cp*)(μ-BH4 )}2 (Fv tttt )] (1, Cp* = C5 Me5 ) is converted into the trimetallic borohydride-bridged species [{Dy(Cp*)(Fv tttt )}2 Dy(μ-BH4 )3 ] (2). In turn, 2 is reacted with a silylium electrophile to give [{Dy(Cp*)(μ-BH4 )(Fv tttt )}2 Dy][B(C6 F5 )4 ] ([3][B(C6 F5 )3 ]), the first trimetallic dysprosocenium cation. Compound [3 ][B(C6 F5 )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.