[5×1 + 1×1] Hexanuclear Lanthanide(III) Cocrystal Complexes: Syntheses, Structures, and Magnetic Properties

Abstract

Syntheses, structures, and magnetic properties of two hexanuclear [5×1 + 1×1] lanthanide cocrystal complexes [Ln5(L)4(LH2)2(tfa)4]·[Ln(tfa)4]·2CH3OH [Ln = Dy(1) and Tb(2)] derived from the polyhydroxy ligand 2‐(hydroxymethyl)‐6‐carbaldehyde‐4‐methylphenol (LH2) are reported. Compounds 1 and 2 crystallize in the triclinic system with space group P1. X‐ray crystallography reveals that 1 and 2 are cocrystals comprising one cationic pentanuclear [Ln5(L)4(LH2)2(tfa)4]+ unit and one anionic mononuclear [Ln(tfa)4]–unit as well as two molecules of methanol as solvent of crystallization. Both complexes form a [2.2] spirocyclic topology fashioned core due to merging of two triangular geometries composed of Ln(III) ions through a common vertex. The central Ln(III) ion in the spirocyclic pentanuclear assembly is eight‐coordinate with distorted square antiprism geometry. On the other hand, the peripheral eight‐coordinate Ln(III) ions are in a distorted trigonal dodecahedron geometry. The comprehensive magnetic study reveals that compound 1 displays slow relaxation of magnetism.

Pentanuclear Spirocyclic Ni4Ln Derivatives: Field Induced Slow Magnetic Relaxation in the Dysprosium and Erbium Analogues

“…To the best of our knowledge, only six pentanuclear Ni–Ln heteronuclear complexes, (Figure ) are found whose detailed magnetic analysis has been done. Although the spirocyclic core is well known in pure 4f based compounds, the case of coordination compounds based on 3d‐4f systems, it is scare. Apart from this work, only two examples are known where spirocyclic shaped core in 3d/4f system has been observed earlier , .…”

Chirality and Magnetic Properties of One‐dimensional Ln (Ln = Gd, Dy) Polymers

“…For Dy , the curve shape of χ M T – T indicates the magnetic interaction between spins is completely different from Gd . At room temperature, the χ M T value is 14.30 cm 3 · K · mol –1 , which corresponds to the expected 14.7 cm 3 · K · mol –1 ( 6 H 15/2 and g = 4/3) for one isolated Dy III ion , . With cooling, χ M T value steadily and brings down to minimum value of 11.74 cm 3 · K · mol –1 at 20.0 K, which is mainly ascribed to the thermal depopulation of Stark sublevels of Dy III ion .…”

“…Lanthanide materials have emanated scientists' a great deal of attention over the last few years, due to which not only own charming structures but can be wildly applied in luminescent sensing, magnetic refrigeration and so on . Apart from above mentioned fascinated structures and extensive applications, scientists pay more attention to the potential applications in magnetic and chiral fields .…”

Interplay between anisotropy and magnetic exchange to modulate the magnetic relaxation behaviours of phenoxo bridged Dy2dimers with axial β-diketonate co-ligands

“…In accordance with the current literature review, it emerges that multidentate Schiff base ligands with distinct coordination environments have been effectively applied in the assembly of polynuclear heterometallic 3d/4f [61][62][63][64][65][66][67][68][69][70][71][72][73][74][75] and homometallic 4f complexes. 57,[76][77][78][79][80][81][82][83][84][85] Utilizing the above-mentioned knowledge, we have applied (E)-2-((pyridin-2-ylmethylene)amino) phenol (LH) in order to construct homometallic lanthanide complexes. The ligand LH hereby used was constructed by a single step synthetic procedure involving the condensation of 2-pyridinecarboxaldehyde with 2-amino phenol.…”