Enhancement of Effective Energy Barrier and Magnetic Blocking Temperature in Tetraoxolene Radical Coupled Dinuclear Dysprosium Complex

A well-judged combination of a high axial ligand field and a bridging radical ligand in a dinuclear lanthanide complex provides a single-molecule magnet with a higher effective energy barrier for magnetic relaxation and blocking temperature compared to its non-radical analog due to significant magnetic exchange coupling between radical and Ln(III) ions. In this work, we report two chloranilate (CA) bridged dinuclear dysprosium complexes, [{(bbpen)Dy(μ₂-CA)Dy(bbpen)}] (1Dy) and [{(bbpen)Dy(μ₂-CA⋅)Dy(bbpen)}^-{CoCp₂}⁺] (2Dy), where 2Dy is the radical bridged Dy-complex obtained via the chemical reduction of bridging CA moiety (H₂bbpen=N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine). The presence of high electronegative phenoxide moiety enhances the axial anisotropy of pseudo-square antiprismatic Dy(III) ions. The diffused spin of radical is efficiently coupled with anisotropic Dy(III) centres and decreases the quantum tunnelling of magnetization (QTM) in the magnetic relaxation process. The magnetic relaxation of 1Dy follows Orbach, Raman, and QTM processes whereas for 2Dy it follows Orbach and Raman Processes. Due to less involvement of the QTM relaxation process, 2Dy shows a higher thermal energy barrier (U_eff=700 K) and a high blocking temperature (6.7 K), compared to its non-radical analog. Remarkably, the radical coupled 2Dy complex shows the highest energy barrier among the radical bridged Dy(III)-based SMMs to date.