New Family of Dinuclear Ni–Ln Complexes from Ternary Coordination by β-Diketonates around the Lanthanoids: Synthesis, Structures, and Magnetic Behavior with Theoretical Supports DOI

Biswarup Dutta,

Thierry Guizouarn,

Amit Gharu

et al.

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 25(1), P. 143 - 157

Published: Dec. 13, 2024

A single-pot synthetic endeavor was utilized with a binucleating phenolate-centered unsymmetrical ligand to obtain two new series of Ni–Ln complexes. The method also facilitated the capping types β-diketonate anions around larger lanthanide ions vacant coordination sites. Using dibenzoylmethane (dbmH) and benzylacetonate (bzaH) as ancillaries, distinct groups complexes, [NiLn(HL)2(dbm)2]NO3 (where Ln = Tb3+ (1a), Dy3+ (1b), Ho3+ (1c)) [NiLn(HL)2(bza)2]NO3·xMeOH Gd3+ (2a), x 3; (2b), 0; (2c), Er3+ (2d), 0) (H2L 2-methoxy-6-[(E)-2′-hydroxymethyl-phenyliminomethyl]-phenol), were obtained in good yields. For complexes 1a–2d, HL– units grab NiII first an elongated octahedral N2O4 geometry apical alcohol OH groups. LnIII centers next caged distorted O8 donor-based square antiprism geometry. Both dc ac magnetic susceptibility measurements demonstrated (i) involvement ferromagnetic interaction between adjacent nickel(II) (S 1) other lanthanoids except HoIII (ii) lack slow relaxation at 2 K zero applied field. computational study using ab initio methods involving CASSCF (Complete Active Space Self-Consistent Field), RASSI-SO (Restricted State Interaction Spin–Orbit), SINGLE_ANISO programs, along POLY_ANISO program, provides detailed insights into properties mechanisms single-ion systems, particularly Theoretical calculations backed experimental results magnetization for 1a–1c 2b–2d field prominent maxima out-of-phase component weak exchange noncollinearity anisotropic axes led significant tunneling gap (Δtun) QTM ground coupled doublet states all that directed even state.

Language: Английский

Preparation and properties of a series of discrete zinc-rare earth heterometallic complexes based on 2,4-dichlorobenzoate and 2,2′-bipyridine DOI

Shu-Fang Zheng,

Jinsheng Zhang, Zhenyu Yang

et al.

Inorganica Chimica Acta, Journal Year: 2025, Volume and Issue: unknown, P. 122644 - 122644

Published: March 1, 2025

Language: Английский

Citations

0
Trinuclear ZnII-LnIII Complexes: Single-Ion Magnet Behavior in the Zn2Dy Analogue DOI
Soumalya Roy,

Botan Li,

Ezhava Manu Manohar

et al.

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Language: Английский

Citations

0
New Family of Dinuclear Ni–Ln Complexes from Ternary Coordination by β-Diketonates around the Lanthanoids: Synthesis, Structures, and Magnetic Behavior with Theoretical Supports DOI

Biswarup Dutta,

Thierry Guizouarn,

Amit Gharu

et al.

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 25(1), P. 143 - 157

Published: Dec. 13, 2024

A single-pot synthetic endeavor was utilized with a binucleating phenolate-centered unsymmetrical ligand to obtain two new series of Ni–Ln complexes. The method also facilitated the capping types β-diketonate anions around larger lanthanide ions vacant coordination sites. Using dibenzoylmethane (dbmH) and benzylacetonate (bzaH) as ancillaries, distinct groups complexes, [NiLn(HL)2(dbm)2]NO3 (where Ln = Tb3+ (1a), Dy3+ (1b), Ho3+ (1c)) [NiLn(HL)2(bza)2]NO3·xMeOH Gd3+ (2a), x 3; (2b), 0; (2c), Er3+ (2d), 0) (H2L 2-methoxy-6-[(E)-2′-hydroxymethyl-phenyliminomethyl]-phenol), were obtained in good yields. For complexes 1a–2d, HL– units grab NiII first an elongated octahedral N2O4 geometry apical alcohol OH groups. LnIII centers next caged distorted O8 donor-based square antiprism geometry. Both dc ac magnetic susceptibility measurements demonstrated (i) involvement ferromagnetic interaction between adjacent nickel(II) (S 1) other lanthanoids except HoIII (ii) lack slow relaxation at 2 K zero applied field. computational study using ab initio methods involving CASSCF (Complete Active Space Self-Consistent Field), RASSI-SO (Restricted State Interaction Spin–Orbit), SINGLE_ANISO programs, along POLY_ANISO program, provides detailed insights into properties mechanisms single-ion systems, particularly Theoretical calculations backed experimental results magnetization for 1a–1c 2b–2d field prominent maxima out-of-phase component weak exchange noncollinearity anisotropic axes led significant tunneling gap (Δtun) QTM ground coupled doublet states all that directed even state.

Language: Английский

Citations

0