Tuning the porosity of lanthanide MOFs with 2,5-pyrazinedicarboxylate and the first in situ hydrothermal carboxyl transfer

Cai, Bin; Yang, Ping; Dai, Jing‐Wei; Wu, Jian‐Zhong

doi:10.1039/c0ce00340a

Cited by 41 publications

(15 citation statements)

References 40 publications

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“…The prediction of the crystal structures made via hydro(solvo)thermal in situ ligand reactions is still a difficult task, it being well-known that unexpected results can occur when hydro(solvo)thermal syntheses are employed (see some selected examples listed in Table S1). ,− For instance, the 2,5-pyrazinedicarboxylate (dianion of 2,5-H 2 pzdc) was obtained in situ under hydrothermal conditions through the oxidation of the methyl group of the initial Hmpca reagent for the series of complexes [Ln 2 (2,5-pzdc) 3 (H 2 O) 4 ]·6H 2 O} n [Ln = Ce ( 1 ), Pr ( 2 ), Nd ( 3 ), and Eu ( 4 )] and {[Er 2 (2,5-pzdc) 3 (H 2 O) 4 ]·5H 2 O} n ( 5 ), which are the subject of this work. Such an oxidation is very attractive, because two carboxylate groups as substituents in the heterocyclic pyrazine ring allow multiple coordination modes as shown in Chart b.…”

Section: Introductionmentioning

confidence: 99%

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks

et al. 2017

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In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln(2,5-pzdc)(HO)]·6HO} [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er(2,5-pzdc)(HO)]·5HO} (5). Single-crystal X-ray diffraction on 1-5 reveals that they crystallize in the triclinic system, P1̅ space group with the series 1-4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc dianions acting as two- and fourfold connectors, building a binodal 4,4-connected (4·68)(468)-mog network. The photophysical properties of the Nd(III) (3) and Eu(III) (4) complexes exhibit sensitized photoluminescence in the near-infrared and visible regions, respectively. The photoluminescence intensity and lifetime of 4 were very sensitive due to the luminescence quenching of the D level by O-H oscillators of four water molecules in the first coordination sphere leading to a quantum efficiency of 11%. Variable-temperature magnetic susceptibility measurements for 1-5 reveal behaviors as expected for the ground terms of the magnetically isolated rare-earth ions [F, H, I, F, and I for Ce(III), Pr(III), Nd(III), Eu(III), and Er(III), respectively] with M = 0 (2 and 4) and ±1/2 (1, 3, and 5). Q-band electron paramagnetic resonance measurements at low temperature corroborate these facts. Frequency-dependent alternating-current magnetic susceptibility signals under external direct-current fields in the range of 100-2500 G were observed for the Kramers ions of 1, 3, and 5, indicating slow magnetic relaxation (single-ion magnet) behavior. In these compounds, τ decreases with decreasing temperature at any magnetic field, but no Arrhenius law can simulate such a dependence in all the temperature range. This dependence can be reproduced by the contributions of direct and Raman processes, the Raman exponent (n) reaching the expected value (n = 9) for a Kramers system.

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Section: Introductionmentioning

confidence: 99%

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks

et al. 2017

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“…Metal-organic frameworks (MOFs) [8][9][10][11][12][13] are compounds consisting of metal ions coordinated to organic ligands such as aromatic substances and derivatives, 14 or nitrogen heterocyclic compounds 15 to form one-, two-, or three-dimensional structures. Compared to conventionally used catalysts, MOFs have large surface area, 16 high thermal and chemical stability, 17 as well as diverse skeleton structures obtained by modulating the functional architecture of the metal ions and the organic ligands.…”

Section: Introductionmentioning

confidence: 99%

Water-mediated promotion of direct oxidation of benzene over the metal–organic framework HKUST-1

Liu

Zhang

et al. 2015

RSC Adv.

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“…Altogether, the cubic MOP assembly of 2 consists of 42 components. There are a few reports in the literature that utilized PZDC ligands as linkers in coordination polymers . However, the construction of MOFs/MOPs based on this ligand remained unexplored.…”

Section: Resultsmentioning

confidence: 99%

Mapping the Assembly of Metal–Organic Cages into Complex Coordination Networks

Yadav

Gupta

Steiner

et al. 2017

Chemistry A European J

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Structural transformations of supramolecular assemblies play an important role in the synthesis of complex metal-organic materials. Nonetheless, often little is known of the assembly pathways that lead to the final product. This work describes the conversion of cubic metal-organic polyhedra to connected-cage networks of varying topologies. The neutral cubic cage assembly of formula {Pd [PO(NiPr) ]} (PZDC) has been synthesized from {Pd [(NiPr) PO](OAc) (OH)} ⋅2 (CH ) SO and 2,5-pyrazenedicarboxilic acid (PZDC-2H). This 42-component self-assembly is the largest known among the neutral cages with Pd ions. The cage contains twenty-four vacant carboxylate O-sites at the PZDC ligands that are available for further coordination. Post-assembly reactions of the cubic cage with Fe and Zn ions produced cage-connected networks of dia and qtz topologies, respectively. During these reactions, the discrete cubic cage transforms into a network of tetrahedral cages that are bridged by the 3D metal ions. The robustness of the [Pd {[PO(NiPr) }] molecular building units made it possible to map the post-assembly reactions in detail, which revealed a variety of intermediate 1D and 2D cage networks. Such step-by-step mapping of the transformation of discrete cages to cage-connected frameworks is unprecedented in the chemistry of coordination driven assemblies.

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Tuning the porosity of lanthanide MOFs with 2,5-pyrazinedicarboxylate and the first in situ hydrothermal carboxyl transfer

Cited by 41 publications

References 40 publications

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks

Water-mediated promotion of direct oxidation of benzene over the metal–organic framework HKUST-1

Mapping the Assembly of Metal–Organic Cages into Complex Coordination Networks

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