TY - JOUR
T1 - Temperature-dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands
AU - Chainok, Kittipong
AU - Ponjan, Nutcha
AU - Theppitak, Chatphorn
AU - Khemthong, Phailyn
AU - Kielar, Filip
AU - Dungkaew, Winya
AU - Zhou, Yan
AU - Batten, Stuart R.
PY - 2018/12/14
Y1 - 2018/12/14
N2 -
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 P1. 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 P2
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 P2
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.
AB -
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 P1. 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 P2
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 P2
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.
UR - http://www.scopus.com/inward/record.url?scp=85057551389&partnerID=8YFLogxK
U2 - 10.1039/c8ce01430b
DO - 10.1039/c8ce01430b
M3 - Article
AN - SCOPUS:85057551389
SN - 1466-8033
VL - 20
SP - 7446
EP - 7457
JO - CrystEngComm
JF - CrystEngComm
IS - 46
ER -