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A bis-calix[4]arene-supported [Cu] cage
Reaction of 2,2′-bis- p - t Bu-calix[4]arene (H 8 L) with Cu(NO 3 ) 2 ·3H 2 O and N -methyldiethanolamine (Me-deaH 2 ) in a basic dmf/MeOH mixture affords [Cu II 16 (L) 2 (Me-dea) 4 (μ 4 -NO 3 ) 2 (μ-OH) 4 (dmf) 3.5 (MeOH) 0.5 (H 2 O) 2 ](H 6 L)·16dmf·4H 2 O ( 4 ), following slow evaporation of the...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2023-07, Vol.52 (26), p.8956-8963 |
|---|---|
| Main Authors: | , , , , , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites |
| Online Access: | Get full text |
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| Summary: | Reaction of 2,2′-bis-
p
-
t
Bu-calix[4]arene (H
8
L) with Cu(NO
3
)
2
·3H
2
O and
N
-methyldiethanolamine (Me-deaH
2
) in a basic dmf/MeOH mixture affords [Cu
II
16
(L)
2
(Me-dea)
4
(μ
4
-NO
3
)
2
(μ-OH)
4
(dmf)
3.5
(MeOH)
0.5
(H
2
O)
2
](H
6
L)·16dmf·4H
2
O (
4
), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu
12
], in which the four capping metal ions are the Cu
II
ions housed in the calix[4]arene polyphenolic pockets. The [Cu
II
8
] square prism is held together "internally" by a combination of hydroxide and nitrate anions, with the
N
-methyldiethanolamine co-ligands forming dimeric [Cu
II
2
] units which edge-cap above and below the upper and lower square faces of the prism. Charge balance is maintained through the presence of one doubly deprotonated H
6
L
2−
ligand per [Cu
16
] cluster. Magnetic susceptibility measurements reveal the predominance of strong antiferromagnetic exchange interactions and an
S
= 1 ground state, while EPR is consistent with a large zero-field splitting.
A [Cu
II
16
] cluster based on a tetra-capped square prism is constructed using 2,2′-bis-
p
-
t
Bu-calix[4]arene. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d3dt01448g |