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Tetranuclear [CuLn] complexes derived from a tetraketone-type ligand
A series of tetranuclear [Cu 3 Ln] complexes, [Cu 3 Gd(L) 3 (NO 3 ) 2 (H 2 O) 3 ](NO 3 )·H 2 O ( 1 ), [Cu 3 Tb(L) 3 (NO 3 ) 2 (H 2 O) 3 ](NO 3 ) ( 2 ) and [Cu 3 Dy(L) 3 (NO 3 ) 3 (H 2 O) 2 ]·1.5(H 2 O) ( 3 ), were synthesized by a one-pot reaction using a simple tetraketone-type ligand (H 2 L = (3 Z...
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Published in: | Dalton transactions : an international journal of inorganic chemistry 2023-03, Vol.52 (13), p.3947-3953 |
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Main Authors: | , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | A series of tetranuclear [Cu
3
Ln] complexes, [Cu
3
Gd(L)
3
(NO
3
)
2
(H
2
O)
3
](NO
3
)·H
2
O (
1
), [Cu
3
Tb(L)
3
(NO
3
)
2
(H
2
O)
3
](NO
3
) (
2
) and [Cu
3
Dy(L)
3
(NO
3
)
3
(H
2
O)
2
]·1.5(H
2
O) (
3
), were synthesized by a one-pot reaction using a simple tetraketone-type ligand (H
2
L = (3
Z
,5
Z
)-4,5-dihydroxy-3,5-octadiene-2,7-dione). X-ray structural analyses revealed that each complex has a planar tetranuclear core of [Cu
3
Ln] (Ln = Gd, Tb, and Dy), in which the Ln ion is accommodated in the centre of a Cu
3
O
6
metallocycle. A cryomagnetic study revealed that all complexes show intramolecular ferromagnetic interactions between Cu(
ii
) and Ln(
iii
) ions. The [Cu
3
Gd] complex (
1
) has an
S
T
= 5 spin ground state and shows a magneto-caloric effect with a maximum magnetic entropy change (-Δ
S
m
) of 16.4 J kg
−1
K
−1
(5 T, 2.4 K). On the other hand, the [Cu
3
Tb] complex (
2
) shows a slow magnetic relaxation behavior under a zero magnetic field. The analysis of an Arrhenius plot reveals that the effective energy barrier of spin reversal is 13.1 K. The [Cu
3
Dy] complex (
3
) also shows a slow magnetic relaxation under 1300 Oe dc magnetic field with an effective energy barrier of 6.82 K.
Tetranuclear [Cu
3
Ln] complexes (Ln = Gd(
iii
), Tb(
iii
), and Dy(
iii
)) with a planar tetranuclear structure were synthesized. The [Cu
3
Gd] complex has an
S
T
= 5 spin ground state and the [Cu
3
Tb] and [Cu
3
Dy] complexes show slow magnetic relaxation. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/d2dt03892g |