Crystal structure of poly[bis(ammonium) [bis(μ<sub>4</sub>-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

Ordonez, Carlos; Fonarı, Marina S.; Wei, Qiang; Timofeeva, Tatiana V.

doi:10.1107/s2056989016007027

Acta Cryst E

2016

DOI: 10.1107/s2056989016007027

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Crystal structure of poly[bis(ammonium) [bis(μ₄-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

Carlos Ordonez

Marina S. Fonarı

Qiang Wei

et al.

Abstract: The title three-dimensional metal–organic framework (MOF) material features an anionic framework constructed from Zn2+ cations and benzene-1,3,5-tricarboxylate (BTC) organic anions. Charge balance is achieved by outer sphere ammonium cations formed by degradation of di-n-butylamine in the solvothermal synthesis of the material.

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Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

Wei

Ordonez

et al. 2018

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In order to assess how metal doping affects the luminescence and magnetic properties of anionic Metal-Organic Frameworks (MOFs), seven single-metal doped MOFs {M-Zn-BTC}{Me 2 NH 2 + } (M = Co, Cu, Ni, Mn, Ca, Mg, Cd) and three dual-metal doped MOFs {Zn-M 1 -M 2 -BTC}{Me 2 NH 2 + } (M 1 = Co, Cu; M 2 = Ni, Co) were synthesized. Trace amounts of different metals were doped via addition of another metal salt during the synthetic process. All compounds retained the same crystal structure as that of the parent {Zn-BTC}{Me 2 NH 2 + } MOF, which was supported by single crystal and powder X-ray diffraction studies. Thermal Gravimetric Analysis (TGA) of these compounds also revealed that all MOFs had similar stability up to~450 • C. Solid state photoluminescent studies indicated that {Zn-Mn-BTC}{Me 2 NH 2 + }, {Zn-Cd-BTC}{Me 2 NH 2 + }, and {Zn-Ca-BTC}{Me 2 NH 2 + } had a significant red shifting effect compared to the original {Zn-BTC}{Me 2 NH 2 + } MOF. Applications of this doping method to other MOF systems can provide an efficient way to tune the luminescence of such systems, and to obtain a desired wavelength for several applications such as sensors and white light LED materials. Because Zn, Co, Cu, Ni, Mg have magnetic properties, the effect of the doping metal atom on the magnetism of the {Zn-BTC}{Me 2 NH 2 + } networks was also studied. To characterize the magnetic behavior of the synthesized MOFs, we conducted low-temperature (10 K) saturation remanence experiments in a 3 Tesla applied field, with the principal goal of identifying the domain state of the synthesized materials (Zn, Zn-Co, Zn-Cu-Co, Zn-Cu-Ni, Zn-Mg, Zn-Mn, Zn-Ni-Co, Zn-Ni). During room/low temperature saturation magnetization experiments, Zn, Zn-Co, Zn-Cu-Co, and Zn-Cu-Ni systems yielded data indicative of superparamagnetic behavior, yet during zero field and field cooled experiments Zn-Co showed a slight paramagnetic effect, Zn showed no temperature dependence on warming and Zn-Cu-Co and Zn-Cu-Ni demonstrated only a slight temperature dependence on warming. These behaviors are consistent with ferromagnetic ordering. Zero field and field cooled experiments indicate that Zn-Mg and Zn-Ni have a ferromagnetic ordering and Zn-Mn and Zn-Ni-Co show paramagnetic ordering behavior.

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Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

Wei

Ordonez

et al. 2018

Crystals

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Crystal structure of poly[bis(ammonium) [bis(μ₄-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

Cited by 1 publication

References 18 publications

Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

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Crystal structure of poly[bis(ammonium) [bis(μ4-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

Cited by 1 publication

References 18 publications

Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

Tuning of Luminescent and Magnetic Properties via Metal Doping of Zn-BTC Systems

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Crystal structure of poly[bis(ammonium) [bis(μ₄-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]