abstract
The fascinating field of 3d-4f single-molecule magnets (SMMs) has gained considerable attention since the breakthrough work of slow relaxation of magnetization in a CuII-TbIII system. In this report, we present the synthesis of three new isostructural and isomorphous [CuLn(L)(NO3)3(H2O)] complexes (Ln = Gd (1), Tb (2), and Dy (3)), derived from a compartmental Schiff base ligand, H2L. To further unravel the magnetic dynamics, we also developed two closely related ZnII-DyIII complexes, [ZnDy(L)(NO3)3(py)] (4) and [ZnDy(L)(OAc)(piv)(NO3)] (5), with py, OAc, and piv representing pyridine, acetate, and pivalate ions, respectively. These complexes offer an opportunity to explore the influence of paramagnetic CuII and diamagnetic ZnII ions on dynamic magnetic behaviors. Magnetic susceptibility measurements indicate a dominant Stark sublevel depopulation effect for the DyIII ions in complexes 4 and 5, alongside pronounced ferromagnetic interactions between the CuII ion and the respective LnIII ions in 1-3, as commonly observed for >= 4f7 ions. Intriguingly, all synthesized complexes exhibit dynamic magnetic behavior in the presence of an applied magnetic field, indicating that the ferromagnetic influence of CuII ions and the charge polarization from the ZnII ion play crucial roles in shaping their magnetic properties. The most important achievement of this study is the observation of field-induced slow relaxation of magnetization in complex 1, despite the isotropic nature of the GdIII ion. Given the scarcity of CuII-GdIII systems demonstrating single-molecule magnet behavior, this work adds a remarkable contribution to the expanding field of GdIII-based SMMs, offering fresh insights and broadening the horizons of future research in this promising area.
keywords
EXCHANGE INTERACTIONS; GD-III; CO-II; DILANTHANIDE COMPLEXES; LANTHANIDE COMPLEXES; DINUCLEAR COMPLEXES; ANISOTROPY BARRIER; CRYSTAL-STRUCTURES; TB-III; DY-III
subject category
Chemistry
authors
Nandy, R; Jana, NC; Jagodic, M; Jaglicic, Z; Brandao, P; Saha, A; Panja, A
our authors
Paula Cristina Ferreira da Silva Brandão
Assistant ResearcherProjects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
A. P. gratefully acknowledges the financial support of this work by the CSIR, New Delhi, India (Sanction no. 01/3118/23/EMR-II dated 08.07.23). Z. J. acknowledges the financial support of the Slovenian Research Agency (Grant No. P2-0348). P. B. gratefully acknowledges the financial support of this work by the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC).