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Cu(II) MOFs Based on Bipyridyls: Topology, Magnetism, and Exploring Sensing Ability toward Multiple Nitroaromatic Explosives.

ABSTRACT: In this work, a series of three copper(II) metal-organic frameworks (MOFs), [Cu(4,4'-DP)Cl] _n (1), [Cu(4,4'-DP)_0.5Cl] _n (2), and [Cu(4,4'-TMDP)Cl] _n (3) (4,4'-DP = 4,4'-dipyridyl, 4,4'-TMDP = 4,4'-trimethylenedipyridyl), is designed and synthesized under solvothermal conditions. Crystallographic investigations reveal that 1 and 2 have tetrahedral and 3 has octahedral environment around the Cu(II) ion. By varying the solvent conditions and ligand derivatives, the topology can be interestingly tuned. TOPOS Pro provides topological conclusions that 1 is stabilized by unusual 2D + 2D ? 3D polycatenation of layers lying in (110) and (11?0) planes with dihedral angle of 90° showing altogether fes , hcb , and sql topologies. On the other hand, 2 exhibits a bey (3,4-c net) topology and 3 shows 4-fold interpenetration with the dia topology. The dc measurements for 1-3 performed on polycrystalline samples in a 0.1 T field confirm strong ferromagnetic behaviors for 1 and 2 and moderate antiferromagnetic behavior for 3. To examine the sensing properties of the three MOFs, various hazardous nitroaromatic compounds (NACs) were used as analytes. While 1 is a potent fluorescence sensor for highly sensitive detection of multiple NACs, 2 selectively detects meta-dinitrobenzene (m-DNB) with K _SV = 5.73 × 10⁵ M^-1 and a remarkably lower limit of detection (LOD) value of 1.23 × 10^-7 M. 3 does not show sensing ability toward any NAC probably due to the coordination environment being different from those in 1 and 2. The work demonstrates fine-tuning of the topology and in turn magnetic and sensing properties by changing the reaction conditions.

SUBMITTER: Ahamad MN

PROVIDER: S-EPMC6648553 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Cu(II) MOFs Based on Bipyridyls: Topology, Magnetism, and Exploring Sensing Ability toward Multiple Nitroaromatic Explosives.

Ahamad M Naqi MN Shahid M M Ahmad Musheer M Sama Farasha F

ACS omega 20190429 4

In this work, a series of three copper(II) metal-organic frameworks (MOFs), [Cu(4,4'-DP)Cl] n (1), [Cu(4,4'-DP)0.5Cl] n (2), and [Cu(4,4'-TMDP)Cl] n (3) (4,4'-DP = 4,4'-dipyridyl, 4,4'-TMDP = 4,4'-trimethylenedipyridyl), is designed and synthesized under solvothermal conditions. Crystallographic investigations reveal that 1 and 2 have tetrahedral and 3 has octahedral environment around the ...[more]

PMID: 31459863

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Project description:A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker (L; bis-[N-(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[b,f][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer (TB-Zn-CP) was synthesized in quantitative yield using Zn(OAc)2·2H2O and tetraacid linker L (1?:?0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m2 g-1. Furthermore, TB-Zn-CP displayed an excellent CO2 uptake capacity of 76 mg g-1 at 273 K and good adsorption selectivity for CO2 over N2 and H2. The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence (?max = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives.

Dataset Information

Cu(II) MOFs Based on Bipyridyls: Topology, Magnetism, and Exploring Sensing Ability toward Multiple Nitroaromatic Explosives.

Publications

Cu(II) MOFs Based on Bipyridyls: Topology, Magnetism, and Exploring Sensing Ability toward Multiple Nitroaromatic Explosives.

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