Self-assembled octanuclear [Ni₅Ln₃] (Ln = Dy, Tb and Ho) complexes: synthesis, coordination induced ligand hydrolysis, structure and magnetism

Abstract

Octanuclear NiII5LnIII3 complexes obtained with ligand H2L show ferromagnetic interactions for Ni5Dy3 and Ni5Tb3 while antiferromagnetic interactions for Ni5Ho3.

Hydroxido supported and differently networked octanuclear Ni6Ln2 [Ln = GdIII and DyIII] complexes: structural variation, magnetic properties and theoretical insights

“…This core formed from six partial fused dicubane units with the participation of six μ 3 -OH − , two μ-OH − and two μ-OH 2 units, which is rare in literature. 25 S2 in the ESI, Fig. 2).…”

“…Use of semi-rigid phenol-based Schiff base ligand system bearing flexible C−N and rigid −C=N sides is presumed to control the hydrolytic aggregation reaction following 3d ion bound initially formed fragments. 25 Herein, 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol (H 2 L) (Fig. S1, ESI) was screened for preferential coordination of Ni II…”

Two SiO44–-Templated Ln23Ni20 Clusters with Magnetic Cooling and Stability

“…19−23 With regard to the ligand-controlled hydrolytic method, according to hard−soft acid−base theory, 3d metal ions are inclined to coordinate with soft atoms (such as S and N), while the 4f metal ions tend to bond with hard atoms (such as O and F). 24,25 At the same time, the organic ligands containing hard and soft atoms are beneficial to establish giant 3d-4f clusters.…”

“…Persistent investigation on the synthetic methods demonstrates suitable ligand and anionic templates are the significant conditions to obtain giant 3d-4f nanoclusters. − With regard to the ligand-controlled hydrolytic method, according to hard–soft acid–base theory, 3d metal ions are inclined to coordinate with soft atoms (such as S and N), while the 4f metal ions tend to bond with hard atoms (such as O and F). , At the same time, the organic ligands containing hard and soft atoms are beneficial to establish giant 3d-4f clusters. For instance, iminodiacetic acid (H 2 IDA) with [N, O, O] donor sites has been widely utilized to construct an extremely diverse family of 3d-4f metal clusters. , Herein, the organic ligand H 2 DTA with multifunctional coordination sites [S, O, O] and a similar structure with H 2 IDA (as depicted in Figure ) is expected to assemble novel high-nuclearity 3d-4f clusters.…”

Selective Coordination of Self-Assembled Hexanuclear [Ni4Ln2] and [Ni2Mn2Ln2] (Ln = DyIII, TbIII, and HoIII) Complexes: Stepwise Synthesis, Structures, and Magnetic Properties

“…A phenol-bearing Schiff base would be an appropriate choice for the synthesis of such 3d–4f coordination aggregates, where the imine N atom binds 3d ions and the O donor atoms coordinates 4f ions. Such an approach has proven to be successful in providing many Ni–Ln and Mn–Ln complexes of varying nuclearity. − In a few reports, 4f metal ions were incorporated into two different 3d metal ions to synthesize 3d–3d′–4f complexes, where one metalloligand usually acts as a paramagnetic spacer. , To date, to the best of our knowledge, there are no reports in which one type of Schiff base can effectively bind three different paramagnetic spin centers.…”