Cadmium-Inspired Self-Polymerization of {LnIIICd2} Units: Structure, Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm, Eu, Tb, Dy, Ho, Er, Yb)

Abstract

A series of heterometallic carboxylate 1D polymers of the general formula [LnIIICd2(piv)7(H2O)2]n·nMeCN (LnIII = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), Yb (7); piv = anion of trimethylacetic acid) was synthesized and structurally characterized. The use of CdII instead of ZnII under similar synthetic conditions resulted in the formation of 1D polymers, in contrast to molecular trinuclear complexes with LnIIIZn2 cores. All complexes 1–7 are isostructural. The luminescent emission and excitation spectra for 2–4 have been studied, the luminescence decay kinetics for 2 and 3 was measured. Magnetic properties of the complexes 3–5 and 7 have been studied; 4 and 7 exhibited the properties of field-induced single-molecule magnets in an applied external magnetic field. Magnetic properties of 4 and 7 were modelled using results of SA-CASSCF/SO-RASSI calculations and SINGLE_ANISO procedure. Based on the analysis of the magnetization relaxation and the results of ab initio calculations, it was found that relaxation in 4 predominantly occurred by the sum of the Raman and QTM mechanisms, and by the sum of the direct and Raman mechanisms in the case of 7.

Low-temperature magnetism of Ln2Ba (Ln = Nd, Er, Ho) furoate-based polymeric chains: Slow relaxation, magnetic anisotropy and interactions

“…AE metals exhibit versatile coordination numbers and potential linkage capabilities. 25,26 Heterometallic coordination compounds formed by lanthanide and alkaline earth metals of diverse dimensionalities have been reported, including trinuclear clusters, 27 1D coordination polymers, 25,28 among which ladder shaped chains, 29 2D structures 28,30 and 3D frameworks. 26 However, previous investigations of 1D AE-Ln-CPs have primarily focused on the luminescent properties of the compounds, with magnetic comprehension notably lacking.…”

The First Tetranuclear Iron(II)‐Gadolinium(III) Carboxylate Complex [Fe2Gd2(piv)10(bpy)2]: Synthesis, Structure Elucidation and Magnetic Properties

“…[22][23][24] One of the promising ligands in the coordination chemistry of 3d-4f-heterometallic complexes is carboxylate ligands (benzoates, acetates, pivalates etc.). [25][26][27][28][29][30] Our investigations in this area are aimed to disclose the structure-properties relationship in the coordination chemistry of heterometallic carboxylates [31][32][33][34][35][36] including polynuclear heterometallic lanthanide derivatives of the types {M 2 Ln} (e. g., M=Zn, Ln=Tb, Eu; M=Co, Ln=La, Gd; M=Cd, Ln=Sm, Eu, Tb, Dy, Ho, Er, Yb) [37][38][39][40][41] and {M 2 Ln 2 } (e. g., M=Zn, Cd, Ln=La; Eu, Nd, Gd, Tb, Dy; M=Cu, Ln=Gd, Tb, Dy, Ho, Yb) [42][43][44][45] supported mainly by different donor ligands: pyridine, [37,40,42] 2,2'-bipyridine, 1,10phenanthroline, [37,40,[42][43][44] triphenylphosphine, [39] N-heterocyclic carbene. [38] Trinuclear {Co 2 Gd} complexes based on pivalic acid and supported by substituted pyridine ligands were found to demonstrate a ferromagnetic exchange Co II À Gd III (J CoÀ Gd = 0.15-0.18 cm À 1 ) which is only weakly affected by the structural changes depending on the type of pyridine ligand.…”