Journal article
A systematic study of halide-template effects in the assembly of lanthanide hydroxide cluster complexes with histidine
Inorganic chemistry frontiers, Vol.8(1), pp.26-34
01/05/2021
DOI: 10.1039/d0qi01004a
Abstract
A series of polynuclear lanthanide (Ln) complexes were prepared by the hydrolysis of lanthanide ions using
l
-histidine as a supporting ligand. Halide ions (X
−
= Cl
−
, Br
−
, and I
−
) have been found to play a major role in templating the assembly of pentadecanuclear complexes for Nd(
iii
) and Gd(
iii
) with the definitive evidence of μ
5
-X
−
in the cluster core formed by five corner-shared cubane units of [Ln
4
(μ
3
-OH)
4
]
8+
. For the heavier and smaller Er(
iii
), analogous pentadecanuclear complex templates by μ
5
-Cl
−
and μ
5
-Br
−
were also isolated, but an otherwise identical reaction in the presence of added I
−
afforded a dodecanuclear complex with a core of four corner-shared cubanes. Two I
−
guests are found, one on each side of the wheel-like structure and in close contact with the μ
3
-OH groups. For the medium size Gd(
iii
), a dodecanuclear complex with two I
−
can also be formed by changing the metal-ligand ratio. The halide-template effects are analyzed, and the production of different cluster complexes can be rationalized by invoking the match of the physical size of the lanthanide and halide ions. The magnetic properties of dodecanuclear
6
were investigated for magnetic cooling applications, and it showed a magnetic entropy change of 30.95 J kg
−1
K
−1
at 2 K for 7 T.
Controlled hydrolysis of lanthanide ions in the presence of histidine and halide templates of different sizes produced dodeca- and pentadecanuclear lanthanide hydroxide clusters.
Details
- Title: Subtitle
- A systematic study of halide-template effects in the assembly of lanthanide hydroxide cluster complexes with histidine
- Creators
- Weiming HuangZhonghao ZhangYinglan WuWanmin ChenDavid A RotschLouis MesserleZhiping Zheng
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry frontiers, Vol.8(1), pp.26-34
- DOI
- 10.1039/d0qi01004a
- ISSN
- 2052-1553
- eISSN
- 2052-1553
- Number of pages
- 9
- Grant note
- DOI: 10.13039/501100001809, name: National Natural Science Foundation of China, award: 21971106
- Date published
- 01/05/2021
- Academic Unit
- Radiology; Chemistry
- Record Identifier
- 9984216583502771
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