Strong Equatorial Crystal Field Enhances the Axial Anisotropy and Energy Barrier for Spin Reversal Process in Yb2 Single Molecule Magnets

Abstract The importance of equatorial crystal fields on magnetic anisotropy of ytterbium single molecule magnets (SMMs) is observed for the first time. Herein, we report three similar dinuclear ytterbium complexes with the formula [Yb 2 (3‐OMe‐L) 2 (DMF) 2 (NO 3 ) 2 ]⋅DMF ( 1 ), [Yb 2 (3‐H‐L) 2 (DMF) 2 (NO 3 ) 2 ]⋅DMF⋅H 2 O ( 2 ), and [Yb 2 (3‐NO 3 ‐L) 2 (DMF) 2 (NO 3 ) 2 ] ( 3 ), [where 3‐X‐H 2 L= N ′‐(2‐hydroxy‐3‐X‐benzylidene)picolinohydrazide, X=OMe ( 1 ), H ( 2 ) NO 2 ( 3 )]. Detailed magnetic measurements reveal the presence of weak antiferromagnetic interactions between the Yb centers and a field‐induced slow relaxation of magnetization in all complexes. A higher energy barrier for spin reversal was observed for complex 1 ( U eff =50 K) and it decreases in the order of 2 (47 K) to 3 (40 K). Notably, complex 1 shows a remarkable energy barrier within the frequency range of 1–850 Hz reported for Yb‐based SMMs. Further, ab initio calculations show a higher axial anisotropy and lower quantum tunneling of magnetization (QTM) in the ground state for 1 compared to 2 and 3 . It was also observed that the presence of a strong crystal field in the equatorial plane (when the ∡ O1−Yb−O3 bond angle is close to 90°) enhances the axial anisotropy and improves the SMM behavior in the studied complexes. Both the experimental and theoretical analysis of relaxation dynamics discloses that Raman and QTM play major role on slow relaxation process for all complexes. To provide more insight into the exchange interactions, broken‐symmetry DFT calculations were performed.