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Cu()-Ln() (Ln = Gd, Tb and Dy) complexes of an unsymmetrical NO donor ligand: field induced SMM behaviour of Cu()-Tb() complexes
Three new hetero-metallic Cu II -Ln III complexes [(CuL)Gd(NO 3 ) 3 (CH 3 OH)] n ( 1 ), [(CuL)Tb(NO 3 ) 3 (H 2 O)]·[CuL] ( 2 ) and [(CuL)Dy(NO 3 ) 3 (H 2 O)]·[CuL] ( 3 ) have been synthesized using a mono-nuclear Cu( ii ) complex, [CuL], of an unsymmetrically di-condensed N 2 O 3 donor Schiff base l...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2024-05, Vol.53 (21), p.9171-9182 |
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| Main Authors: | , , , , , |
| Format: | Article |
| Language: | |
| Online Access: | Get full text |
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| Summary: | Three new hetero-metallic Cu
II
-Ln
III
complexes [(CuL)Gd(NO
3
)
3
(CH
3
OH)]
n
(
1
), [(CuL)Tb(NO
3
)
3
(H
2
O)]·[CuL] (
2
) and [(CuL)Dy(NO
3
)
3
(H
2
O)]·[CuL] (
3
) have been synthesized using a mono-nuclear Cu(
ii
) complex, [CuL], of an unsymmetrically di-condensed N
2
O
3
donor Schiff base ligand,
N
-(3-methoxysalicylidene)-
N
-(salicylidene)-1,2-ethylenediamine (H
2
L). Single crystal X-ray crystallography revealed that complex
1
is a nitrate bridged 1D chain of dinuclear Cu(
ii
)-Gd(
iii
) units whereas in
2
and
3
, the dinuclear Cu(
ii
)-Ln(
iii
) units are co-crystallized with a [CuL] unit. The Ln(
iii
) centers are nine coordinated with the geometry of a spherical capped square antiprism for Gd and spherical tricapped trigonal prism for Tb and Dy. The geometry of the Cu(
ii
) center is distorted octahedral for complex
1
and distorted square planar for complexes
2
and
3
. Temperature-dependent molar magnetic susceptibility measurements in
1-3
revealed the presence of overall ferromagnetic coupling between the Cu(
ii
) and Ln(
iii
) centers. Notably, field induced single-molecule magnet behavior was witnessed in the Tb(
iii
) derivative (
2
). The
ab initio
calculations indicated that upon application of an external magnetic field, the tunneling in the ground state of complex
2
gets reduced and thereby field-induced SMM behaviour is observed. Besides, in the case of complex
1
, BS-DFT calculations were carried out to gain further insights into the magnetic exchange coupling interactions between the Cu(
ii
) and Gd(
iii
) centers.
Among three rare types of Cu
II
-Ln
III
(Ln = Gd, Tb, and Dy) complexes of an unsymmetrical N
2
O
3
donor ligand, only the Tb
III
derivative shows SMM behavior under a dc field. Theoretical calculations explain the magnetic behavior of the complexes. |
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| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d4dt00304g |