Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligandsElectronic supplementary information (ESI) available. CCDC 1863664-1863677. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8ce01430b
Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum) 1.5 (H 2 O) 2 ]·0.5(H 2 bdc)·H 2 O (Ln = Sm ( 1 ), Tb ( 2 )), [Ln 2 (fum) 2 (bdc)(H 2 O) 4 ]·2H 2 O (Ln = Sm ( 3 ), Eu ( 4 ), Tb ( 5 ), Er ( 6 )), [Ln(fum) 0.5 (bdc)] (Ln = Sm ( 7 ), Eu...
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| Main Authors | , , , , , , , |
|---|---|
| Format | Journal Article |
| Published |
26.11.2018
|
| Online Access | Get full text |
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| Summary: | Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum)
1.5
(H
2
O)
2
]·0.5(H
2
bdc)·H
2
O (Ln = Sm (
1
), Tb (
2
)), [Ln
2
(fum)
2
(bdc)(H
2
O)
4
]·2H
2
O (Ln = Sm (
3
), Eu (
4
), Tb (
5
), Er (
6
)), [Ln(fum)
0.5
(bdc)] (Ln = Sm (
7
), Eu (
8
), Tb (
9
), Er (
10
)), and [Ln
2
(bdc)
2
(ox)(H
2
O)
4
]·0.7H
2
O (Ln = Sm (
11
), Gd (
12
), Tb (
13
), Dy (
14
)), have been synthesized hydrothermally from the self-assembly of lanthanide(
iii
) ions (Ln
3+
), fumaric acid (H
2
fum), and terephthalic acid (H
2
bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds
1
and
2
were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group
P
1&cmb.macr;. The 3D framework is assembled from 2D layers of [Ln(fum)(H
2
O)
2
] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H
2
bdc and lattice H
2
O molecules. The framework presents a binodal (4,5)-connected
tcs
topology with the point symbol (4
4
·6
2
)(4
4
·6
6
). Raising the reaction temperature to 140 °C resulted in the formation of compounds
3-6
. These materials crystallize in the monoclinic system with the polar space group
P
2
1
and feature a 3D network constructed from dinuclear {Ln
2
(OCO)
6
(H
2
O)
4
} units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated
pcu
topology. The small channels of the framework are occupied by lattice H
2
O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds
7-10
, crystallizing in the orthorhombic space group
Pbca
. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)]
2+
bound by bdc ligands and contains no intercalated H
2
O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (4
2
·6
4
)
2
(4
6
·6
8
·8)(4
12
·6
9
)
2
. Finally, compounds
11-14
contained an
in situ
generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group
P
2
1
/
c
and possess a 3D open framework consisting of a dinuclear [Ln
2
(ox)(H
2
O)
4
]
2+
unit linked by bridging bdc ligands and has small void channels occupied by lattice H
2
O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected
tcj
/
hc
net with a total point symbol of (4
2
·5
2
·7
2
)(4
2
·5
3
·7
5
). In the solid state at room temperature, the Tb (
2
,
5
,
9
, and
13
) and Eu (
4
and
8
) compounds emit green and red light, respectively.
Four families of fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands have been synthesized hydrothermally at different temperatures. |
|---|---|
| Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 1863664-1863677 10.1039/c8ce01430b |
| ISSN: | 1466-8033 |
| DOI: | 10.1039/c8ce01430b |