TY - JOUR
T1 - Crystal structures, gas storage and magnetic properties of lanthanide-organic frameworks built up from dicarboxylates, [Ln2(2,5-pydc)2(2,5-pipdc)(H2O)2]n (Ln = Ce, Pr, Eu) and (H2pip)n[Ln2(2,6-pydc)4(H2O)2]n (Ln = Ce, Pr, Eu, Sm)
AU - Ay, Burak
AU - Yildiz, Emel
AU - Enomoto, Masaya
AU - Okazawa, Atsushi
AU - Kojima, Norimichi
N1 - Funding Information:
The authors gratefully acknowledge financial support from the Research Unit of Çukurova University (Grant No. FEF-2013-D5 and FÖA-2017-5867 ). The authors also gratefully acknowledge Prof. Hiroshi Kitagawa and Assoc. Prof. Yukihiro Yoshida (Kyoto University, Japan) for their support in the gas storage analyses.
Funding Information:
The authors gratefully acknowledge financial support from the Research Unit of Çukurova University (Grant No. FEF-2013-D5 and FÖA-2017-5867). The authors also gratefully acknowledge Prof. Hiroshi Kitagawa and Assoc. Prof. Yukihiro Yoshida (Kyoto University, Japan) for their support in the gas storage analyses.
Publisher Copyright:
© 2022 Elsevier Ltd
PY - 2022/11/1
Y1 - 2022/11/1
N2 - We have synthesized various kinds of lanthanide complexes, [Ln2(2,5-pydc)2(2,5-pipdc)(H2O)2]n (Ln = Ce (MOF 1), Pr (MOF 2), Eu (MOF 3); 2,5-pydc = 2,5-pyridinedicarboxylate, 2,5-pipdc = 2,5-piperazinedicarboxylate), and (H2pip)n[Ln2(2,6-pydc)4(H2O)2]n (Ln = Ce (MOF 4), Pr (MOF 5), Eu (MOF 6), Sm (MOF 7); 2,6-pydc = 2,6-pyridinedicarboxylate, H2pip = piperazinediium) under hydrothermal conditions. The X-ray crystallographic analysis shows that [Ln2(2,5-pydc)2(2,5-pipdc)(H2O)2]n forms three-dimensional coordination network, while (H2pip)n[Ln2(2,6-pydc)4(H2O)2]n forms one-dimensional coordination polymer, whose different coordination network structure is controlled by the positional isomer of pyridinedicarboxylate (2,5-pydc, 2,6-pydc). The magnetic properties and gas storage (H2 and CO2) capacities were also investigated, and among the synthesized compounds MOF 7 had the highest gas storage capacities for H2 and CO2. From the analysis of magnetic susceptibility measurements, the Weiss constants for Ce, Pr, and Sm complexes were estimated. In the case of Pr complexes, MOF 2 and MOF 5, the magnetic susceptibility deviates from the Curie-Weiss law below 20 K and 10 K, respectively, which is the precursor phenomenon of antiferromagnetic ordering. In the case of Sm(III) complex, MOF 7, the magnetic susceptibility multiplied by temperature (χT) as a function of temperature between 300 K and 2 K was theoretically analyzed and the spin-orbit coupling constant (λ) and the energy levels of ground multiplet, 6HJ, were determined.
AB - We have synthesized various kinds of lanthanide complexes, [Ln2(2,5-pydc)2(2,5-pipdc)(H2O)2]n (Ln = Ce (MOF 1), Pr (MOF 2), Eu (MOF 3); 2,5-pydc = 2,5-pyridinedicarboxylate, 2,5-pipdc = 2,5-piperazinedicarboxylate), and (H2pip)n[Ln2(2,6-pydc)4(H2O)2]n (Ln = Ce (MOF 4), Pr (MOF 5), Eu (MOF 6), Sm (MOF 7); 2,6-pydc = 2,6-pyridinedicarboxylate, H2pip = piperazinediium) under hydrothermal conditions. The X-ray crystallographic analysis shows that [Ln2(2,5-pydc)2(2,5-pipdc)(H2O)2]n forms three-dimensional coordination network, while (H2pip)n[Ln2(2,6-pydc)4(H2O)2]n forms one-dimensional coordination polymer, whose different coordination network structure is controlled by the positional isomer of pyridinedicarboxylate (2,5-pydc, 2,6-pydc). The magnetic properties and gas storage (H2 and CO2) capacities were also investigated, and among the synthesized compounds MOF 7 had the highest gas storage capacities for H2 and CO2. From the analysis of magnetic susceptibility measurements, the Weiss constants for Ce, Pr, and Sm complexes were estimated. In the case of Pr complexes, MOF 2 and MOF 5, the magnetic susceptibility deviates from the Curie-Weiss law below 20 K and 10 K, respectively, which is the precursor phenomenon of antiferromagnetic ordering. In the case of Sm(III) complex, MOF 7, the magnetic susceptibility multiplied by temperature (χT) as a function of temperature between 300 K and 2 K was theoretically analyzed and the spin-orbit coupling constant (λ) and the energy levels of ground multiplet, 6HJ, were determined.
KW - Coordination polymers
KW - Gas storage
KW - Hydrothermal synthesis
KW - MOFs
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U2 - 10.1016/j.poly.2022.116110
DO - 10.1016/j.poly.2022.116110
M3 - Article
AN - SCOPUS:85137092331
SN - 0277-5387
VL - 226
JO - Polyhedron
JF - Polyhedron
M1 - 116110
ER -