Loading…

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...

Full description

Saved in:
Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2023-03, Vol.52 (13), p.3947-3953
Main Authors: Shiga, Takuya, Miyamoto, Haruka, Okamoto, Yukiko, Oshio, Hiroki, Mihara, Nozomi, Nihei, Masayuki
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
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.
ISSN:1477-9226
1477-9234
DOI:10.1039/d2dt03892g