Trinuclear [Co^III₂–Ln^III] (Ln=Tb, Dy) Single‐Ion Magnets with Mixed 6‐Chloro‐2‐Hydroxypyridine and Schiff Base Ligands

Abstract

The Schiff base ligand N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H(2)valdien) and the co-ligand 6-chloro-2-hydroxypyridine (Hchp) were used to construct two 3d-4f heterometallic single-ion magnets [Co(2) Dy(valdien)2 (OCH(3))(2) (chp)(2)]⋅ClO(4)⋅5 H(2)O 1 and [Co(2) Tb(valdien)(2) (OCH(3))(2)(chp)(2)]⋅ClO(4)⋅(2) H(2)O⋅CH(3)OH(2). The two trinuclear [Co(III) 2 Ln(III)] complexes behave as a mononuclear Ln(III) magnetic system because of the presence of two diamagnetic cobalt(III) ions. Complex 1 has a molecular symmetry center, and it crystallizes in the C2/c space group, whereas complex 2 shows a lower molecular symmetry and crystallizes in the P(2)1/c space group. Magnetic investigations indicated that both complexes are field-induced single-ion magnets, and the Co(III)(2)-Dy(III) complex possesses a larger energy barrier [74.1(4.2) K] than the Co(III)(2) -Tb(III) complex [32.3(2.6) K].

Slow Magnetic Relaxation in a Co2Dy Trimer and a Co2Dy2 Tetramer

“… The three types of topologies with their cluster core topology previously reported for Co III 2 Dy III O 4 clusters: bent (up) and triangular (down) [5,10,7,37] …”

“…Complex 1 can be classified as linear since the Co−Dy−O angle is 176.65° (Figure 1) and it is the first example of a linear Co−Dy−Co complex with a Co III 2 Dy III O 4 core structure (Figure 3). [5,10,7] Besides the geometry of the trimers, the main difference between them is the coordination geometry and number around the Dy(III) ion. As can be seen in Table 1, the coordination geometry of the Dy(III) ions in the eight reported Co III 2 Dy III complexes (including complex 1 ) are all different (except for the two octahedral examples).…”

CO2‐fixation into carbonate anions for the construction of 3d‐4f cluster complexes with salen‐type Schiff base ligands: from molecular magnetic refrigerants to luminescent single‐molecule magnets

“…We are also interested in the 3d‐4f cluster‐based SMMs [ 8 ] and cryogenic molecular magnetic refrigerants. [ 9 ] Recently, we mainly studied 3d‐4f cluster complexes with Zn (II) Schiff base building blocks, because they can construct Zn 2 Dy cluster complexes with good SMM properties.…”

Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One

“…A weak SMM behavior was detected for gadolinium, terbium, and dysprosium compounds Molecules 2020, 25, 846 3 of 23 with copper and hp − [13]. A single ion magnet behavior was also observed in two bimetallic (Co(III), Ln(III) = Tb, Dy) complexes with Schiff base ligands and the terminal O-donor ligation of chp − to lanthanide ions [14].No manganese or nickel complexes with Hhp and its molecular or anionic derivatives were characterized at the time of an excellent review by Rawson et al in 1995 [15]. Since then, a few manganese and many nickel polynuclear complexes with hp − , chp − and mhp − achieving various coordination modes have been synthesized in the search for compounds with special magnetic properties.…”

“…A weak SMM behavior was detected for gadolinium, terbium, and dysprosium compounds Molecules 2020, 25, 846 3 of 23 with copper and hp − [13]. A single ion magnet behavior was also observed in two bimetallic (Co(III), Ln(III) = Tb, Dy) complexes with Schiff base ligands and the terminal O-donor ligation of chp − to lanthanide ions [14].…”