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Hexanuclear Co 4 Dy 2 , Zn 4 Dy 2 , and Co 4 Y 2 Complexes with Defect Tetracubane Cores: Syntheses, Structures, and Magnetic Properties
Author(s) -
Li Dawei,
Li Yafei,
Tello Yepes David Felipe,
Zhang Xiamei,
Li Yahong,
Yao Jinlei
Publication year - 2021
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202100571
Subject(s) - crystallography , ion , chemistry , molecule , cluster (spacecraft) , crystal structure , metal , ligand (biochemistry) , lanthanide , metal ions in aqueous solution , stereochemistry , biochemistry , receptor , organic chemistry , computer science , programming language
A hexanuclear heterometallic cluster of composition [Dy 2 Co 4 (L) 4 (NO 3 ) 2 (OH) 4 (C 2 H 5 OH) 2 ] ⋅ 2 C 2 H 5 OH ( 1 ) was synthesized by employing a Schiff base 2‐(((2‐hydroxy‐3‐methoxybenzyl) imino)methyl)‐4‐methoxyphenol (H 2 L) as ligand and utilizing Dy(NO 3 ) 3 ⋅ 6H 2 O and Co(NO 3 ) 2 ⋅ 6H 2 O as metal ion sources. X‐ray single‐crystal diffraction analysis indicated that complex 1 contains a defect tetracubane core and possesses central symmetric structure, with two Dy III ions being in the central body position of the molecule and four Co II ions being arranged at the outer sites. Magnetic studies reveal that complex 1 behaves as single‐molecule magnet (SMM) with energy barrier of 27.50 K. To investigate the individual contribution of Dy III and Co II ions to the SMM behavior, another two complexes of formulae [Dy 2 Zn 4 (L) 4 (NO 3 ) 2 (OH) 4 ] ⋅ 4CH 3 OH ( 2 ) and [Y 2 Co 4 (L) 4 (NO 3 ) 2 (OH) 4 (C 2 H 5 OH) 2 ] ⋅ 2 C 2 H 5 OH ( 3 ) were prepared. Complexes 1 and 3 are isomorphous. The coordination geometries of Dy III ions in 1 and 2 are different. The Dy III ions are eight‐coordinated in 2 and nine‐coordinated in 1 . Complex 2 exhibits SMM behavior with energy barrier of 69.67 K, but complex 3 does not display SMM property. These results reveal that the SMM behaviors of 1 and 2 are mainly originated from Dy III ions. It might be the higher symmetry of Dy III ions in 2 that results in the higher energy barrier.