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Copper()-lanthanide() heterometallic metal-organic frameworks constructed from 3-(3-pyridyl)acrylic acid: syntheses, structures, and properties
The first employment of 3-(3-pyridyl)acrylic acid (3-HPYA) in 3d-4f coordination chemistry is reported. Hydrothermal reactions of 3-HPYA with lanthanide oxides and copper halides led to the formation of 17 novel copper( i )-lanthanide( iii ) heterometallic coordination compounds with four structural...
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| Published in: | CrystEngComm 2016-01, Vol.18 (29), p.5547-5561 |
|---|---|
| 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: | The first employment of 3-(3-pyridyl)acrylic acid (3-HPYA) in 3d-4f coordination chemistry is reported. Hydrothermal reactions of 3-HPYA with lanthanide oxides and copper halides led to the formation of 17 novel copper(
i
)-lanthanide(
iii
) heterometallic coordination compounds with four structural types, namely, [Ln(3-PYA)
3
Cu
3
Cl
3
(H
2
O)
2
]·H
2
O [Ln = Dy (
1
), Eu (
2
), Gd (
3
), Tb (
4
)] (I), [Ln(3-PYA)
3
CuI(H
2
O)
2
]·0.5H
2
O [Ln = Dy (
5
), Gd (
6
), Tb (
7
), Sm (
8
)] (II), [Ln(3-PYA)
3
CuBr(H
2
O)
2
]·
x
H
2
O [Ln = La (
9
), Eu (
10
),
x
= 1; Sm (
11
), Nd (
12
),
x
= 0.5] (II), [LnCu
2
(3-PYA)
2
I
2
(ox)
0.5
(H
2
O)
2
]·(H
2
O)
2
[Ln = Eu (
13
), Gd (
14
), Nd (
15
)] (III) and [LnCu
2
(3-PYA)
2
Br
2
(ox)
0.5
(H
2
O)]·(H
2
O) [Ln = Gd (
16
), Tb (
17
)] (IV) (ox = oxalate). These compounds were thoroughly characterized by single crystal and powder X-ray diffraction, as well as elemental analyses, FT-IR spectroscopy and thermal studies. All the compounds are constructed from halide-containing copper-inorganic motifs and Ln-containing motifs. Compounds of type I are constructed from 1D zigzag Dy-organic chains with [Cu
6
Cl
6
] ladder-like clusters, exhibiting a 2D binodal (5, 6)-connected topology. An unusual chemical rearrangement from [Cu
6
Cl
6
] to [Cu
2
Br
2
]/[Cu
2
I
2
] clusters occurs in the formation of type II structures. They are isostructural and exhibit a 3D coordination framework based on dinuclear [Dy
2
O
2
] subunits and [Cu
2
Br
2
]/[Cu
2
I
2
] clusters as nodes, possessing a binodal (4, 6)-connected net. In the type III structure, the Ln-organic motifs propagate along the
b
-axis, while the Cu-inorganic motifs propagate in the perpendicular direction along the
a
-axis, both of which are further interconnected to give unique 3D (3, 3, 4, 4, 6)-connected nets with {4
2
·6}2{4
2
·8
2
·10
10
·12}{4
3
·6
2
·8}4{4
3
}2 topologies. The type IV structure, based on structural analysis results, features a non-interpenetrated 3D coordination framework containing 2D Ln-organic layers and Cu
2
Br
2
chains with a new 5-nodal (3, 3, 4, 4, 8)-connected topology net (point symbol: {4
2
·6}2{4
3
·6
3
}4{4
3
}2{4
6
·6
10
·8
10
·10
2
}). Our present work represents the first example of heterometallic Cu(
i
) halide-Ln(
iii
)-organic frameworks utilizing 3-HPYA as an organic ligand. The diversity of the products demonstrates that the anion, pH value and reaction temperature have significant effects on the construction of the structures. Mo |
|---|---|
| ISSN: | 1466-8033 1466-8033 |
| DOI: | 10.1039/c6ce00637j |