Tuning the Ferrotoroidic Coupling and Magnetic Hysteresis in Double‐Triangle Complexes {Dy3MIIIDy3} via the MIII‐linker. Issue 5 (23rd December 2020)

• Record Type: Journal Article
• Authors: Ashtree, Jared M.; Borilović, Ivana; Vignesh, Kuduva R.; Swain, Abinash; Hamilton, Sarah H.; Whyatt, Yasmin L.; Benjamin, Sophie L.; Phonsri, Wasinee; Forsyth, Craig M.; Wernsdorfer, Wolfgang; Soncini, Alessandro; Rajaraman, Gopalan; Langley, Stuart K.; Murray, Keith S.
• Is Part Of: European journal of inorganic chemistry. Issue 5(2021)
• Page Start: 435
• Page End: 444
• Publication Date: 2020-12-23
• Subjects: Ab initio calculations -- Heterometallic complexes -- Dysprosium -- Magnetic properties -- Toroics; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202001082
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: We present the syntheses, structures, magnetic data and theoretical analyses for two families of heptanuclear clusters, wherein two staggered dysprosium(III) triangles are linked by various M(III) d‐/p‐block ions. The families differ in the counter‐anion and are of formulae [Dy III 6 M III (OH)8 ( o ‐tol)12 (MeOH)5 (NO3 )] ⋅ 4MeOH and [Dy III 6 M III (OH)8 ( o ‐tol)12 (MeOH)6 ]Cl ⋅ 6MeOH (M=Cr, Mn, Fe, Co, Al; o ‐tol= o ‐toluate). We find that variation of the central metal ion M is crucial in tuning the toroidal moments on the triangular units, with diamagnetic M linking ions enhancing the ferrotoroidic coupling. By detailed simulation and analysis of various magnetic measurements, including sub‐kelvin microSquid hysteresis loops, we identified the specific signature of the M linking ions' modulation of toroidal properties, including the mechanism whereby anisotropic, paramagnetic M ions lead to hysteresis profiles with larger remnant magnetisations and broader coercive fields. Abstract : Experimental data, ab initio calculations and parameter‐free models explore strategies to tune ferro‐ and antiferrotoroidic ground states, implemented in a series of double‐triangle complexes {Dy3 M III Dy3 } with various M ions, counter‐anions and symmetries. Mechanistic studies and simulations of hysteresis reveal how level crossings' positions determine whether complexes display slow magnetic relaxation.