Temperature-dependent studies of [(CH3)2NH2][FeIIIMII(HCOO)6] frameworks (MII = Fe and Mg): structural, magnetic, dielectric and phonon properties

Ciupa, Aneta; Mączka, Mirosław; Gągor, Anna; Sieradzki, Adam; Trzmiel, Justyna; Pikul, Adam; Ptak, Maciej

doi:10.1039/c5dt00512d

Cited by 57 publications

(73 citation statements)

References 40 publications

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“…similar to that observed previously for DMFeMg,22 i.e. the band corresponding to the ρ(NH 2 ) mode exhibits significant shift upon cooling but its FWHM changes weakly (seeFigures 7 and 8).…”

supporting

confidence: 84%

“…It worth adding that although majority of internal modes of DMFeCu are observed in a very similar wavenumber range as the corresponding modes in trigonal niccolites, there is one interesting exception, that is, the ρ(NH 2 ) mode. This mode is observed in all trigonal compounds near 852-855 cm -1 (see Table S7 and [22]). This mode is not well visible for DMFeCu at room temperature but our low-temperature studies (see next paragraph) clearly indicate that it is overlapped by the ν s (CNC) band, i.e., it is observed near 880 cm -1 .…”

Section: Vibrational Properties At Room Temperaturementioning

confidence: 79%

“…22). It worth adding that although majority of internal modes of DMFeCu are observed in a very similar wavenumber range as the corresponding modes in trigonal niccolites, there is one interesting exception, that is, the ρ(NH 2 ) mode.…”

Section: Vibrational Properties At Room Temperaturementioning

confidence: 88%

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Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)

et al. 2015

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We report the synthesis, X-ray diffraction, thermal, magnetic, Raman and IR studies of three heterometallic MOFs, [(CH3)2NH2][Fe(III)M(II)(HCOO)6] with M = Zn (DMFeZn), Ni (DMFeNi) and Cu (DMFeCu), crystallizing in the niccolite type structure. DMFeZn and DMFeNi crystallize in the trigonal structure (space group P3[combining macron]1c) while DMFeCu crystallizes in the monoclinic structure (space group C2/c). Magnetic investigation shows that DMFeZn remains paramagnetic down to the lowest temperature obtained in our experiment while DMFeNi and DMFeCu exhibit ferromagnetic order below 42 and 28.5 K, respectively. IR and Raman data confirm the structural model of the monoclinic DMFeCu and show evidence for stronger hydrogen bonds when compared to trigonal DMFeZn and DMFeNi. A different hydrogen bond network in the monoclinic DMFeCu when compared to trigonal DMFeZn and DMFeNi is responsible for the different behavior of these compounds upon cooling, that is, DMFeCu exhibits a sign of short range ordering of dimethylammonium cations at low temperatures while the trigonal analogues show evolution of dynamic disorder into static disorder.

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confidence: 84%

Section: Vibrational Properties At Room Temperaturementioning

confidence: 79%

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Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)

et al. 2015

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“…33,78 The semiionic C-F bond ensures the highly electronic conductivity and transport property of FNG due to the maintained sp 2 hybridization of this C-F bond. 84,85 In addition, the recent theoretical studies reveals that C-F bonds tend to locate in the vicinity of N-doped region and positively charged C atoms connecting to the F atoms where the C-F bond is polarized as C δ+ -F δrepulse Li ions to the electrochemical active pyridine-and pyrrolic-N sites in neighbourhood that contribute to the conjugated system with a pair of p-electrons in the graphene layer, which facilitate Li ion extraction from/insertion into the electrode during cycling and hence improve the rate capability as well as cycling performance of FNG. 84,85 In addition, the recent theoretical studies reveals that C-F bonds tend to locate in the vicinity of N-doped region and positively charged C atoms connecting to the F atoms where the C-F bond is polarized as C δ+ -F δrepulse Li ions to the electrochemical active pyridine-and pyrrolic-N sites in neighbourhood that contribute to the conjugated system with a pair of p-electrons in the graphene layer, which facilitate Li ion extraction from/insertion into the electrode during cycling and hence improve the rate capability as well as cycling performance of FNG.…”

Section: 63mentioning

confidence: 99%

Nitrogen and fluorine co-doped graphene as a high-performance anode material for lithium-ion batteries

et al. 2015

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Supplementary InformaƟon (ESI) available: FT-IR spectrum, Raman spectrum, XRD patterns, XPS survey spectra, TEM and SEM images, the first three CV curves, Cycle performance, and rate capabilities of NG and RGO See Nitrogen and fluorine co-doped graphene (NFG) with the N and F content as high as 3.24 and 10.9 at.% was prepared through the hydrothermal reaction of trimethylamine tri(hydrofluoride) [(C2H5)3N·3HF] and aqueous-dispersed graphene oxide (GO) as the anode material for lithium ion batteries (LIBs). The N and F co-doping in graphene increased the disorder and defects of the framework, enlarged the space of the interlayer, wrinkled the nanosheets with many open-edge sites, and thus faciliated Li ion diffusion through the electrode compared with sole-N or F doped graphene. X-ray photoelectron spectroscopy (XPS) analysis of NFG demonstrated the presence of active pyridine and pyrrolic types N, and highly electrical conductive graphitic N and semi-ionic C-F bond in the structure. The N and F doping content and the component types of N and F functional groups could be controlled by the hydrothermal temperature. The NFG prepared at 150°C exhibited the best electrochemical performances tested as the anode of LIBs, including the high coulombic efficiency in the first cycle (56.7%), superior reversible specific discahrge capacity (1075 mAh g −1 at 100 mA g −1 ), excellent rate capabilities (305 mAh g −1 at 5 A g −1 ), and outstanding cycling stability (capacity retention of ~95% at 5 A g −1 after 2000 cycles), which demonstrated NFG was a promising candidate for anode materials of high-rate LIBs. 18,20,25 Recently, it has been realized that doping graphene with two or more kinds of heteroatoms can further improve its electrochemical performances because Li-ion storage is not only related with the contents of heteroatoms but also with

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“…The doubleperovskites thus formed, with TM ions of differing d-orbital configurations, can not only result in larger magnetization but can also enhance the strength of the exchange coupling interactions pushing the transition temperature higher. However, only a few studies have so far appeared that explore this strategy [20][21][22][23]. In particular, B-site doping in perovskite MOFs aimed at improving ferroic properties is nascent [24][25][26].…”

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confidence: 99%

Giant ferrimagnetism and polarization in a mixed metal perovskite metal-organic framework

Rout

Srinivasan

2018

Phys. Rev. Materials

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Perovskite metal-organic frameworks (MOFs) have recently emerged as potential candidates for multiferroicity. However, the compounds synthesized so far possess only weak ferromagnetism and low polarization. Additionally, the very low magnetic transition temperatures (Tc) also pose a challenge to the application of the materials.We have computationally designed a mixed metal perovskite MOF -[C(NH2)3][(Cu0.5Mn0.5)(HCOO)3]-that is predicted to have magnetization two orders of magnitude larger than its parent ([C(NH2)3][Cu(HCOO)3]), a significantly larger polarization (9.9 µC/cm 2 ), and an enhanced Tc of up to 56 K, unprecedented in perovskite MOFs. A detailed study of the magnetic interactions revealed a novel mechanism leading to the large moments as well as the increase in the Tc. Mixing a non-Jahn-Teller ion (Mn 2+ ) into a Jahn-Teller host (Cu 2+ ) leads to competing lattice distortions which are directly responsible for the enhanced polarization. The MOF is thermodynamically stable as evidenced by the computed enthalpy of formation, and can likely be synthesized. Our work represents a first step towards rational design of multiferroic perovskite MOFs through the largely unexlpored mixed metal approach.Multiferroics are materials which possess ferromagnetic (FM), ferroelectric (FE) and structural order parameters within a single phase [1][2][3][4][5][6][7][8]. These are highly promising not only for their use in multi-functional device applications but also for the interesting physics they reveal. Much of the research in the field has so far focussed on multiferroics based on inorganic transition metal oxides. In the last decade, there has been growing interest in metal-organic frameworks (MOFs) consisting of metal ions interconnected by organic linkers. The organic-inorganic duality in MOFs leads to many interesting physical properties [9,10] that can be exploited in applications such as gas storage and separation, catalysis, nonlinear optics, photoluminescence, magnetic and electric materials, and so on [11,12]. The hybrid nature of these materials offers a vast chemical space for synthetic chemists to explore and, hence, also affords tunability of properties. MOFs with the perovskite ABX 3 structure are of great interest, particularly those with multiferroic behavior arising due to hydrogen-bonds [13,14]. In the case of magnetic MOFs, for instance, one can control the nature of magnetic coupling through the variety of possible metal ions in the B-site, short ligands, co-ligands and radical ligands carrying spin degrees of freedom [15]. Recently, it has been shown that one can tune the magnitude of the ferroelectric polarization by carefully choosing different A-site cations in these MOFs [16].In recent past, a new class of ABX 3 metal formates [C(NH 2 ) 3 ][M(HCOO) 3 ] (abbreviated below as M-MOF, M= divalent Mn, Fe, Co, Ni, Cu, and Zn), was experimentally synthesized [17]. Of these only the Cu-MOF crystallizes into a polar space group (Pna2 1 ) and exhibits multiferroic and magnetoelectric behavior. It has...

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Temperature-dependent studies of [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] frameworks (M^II = Fe and Mg): structural, magnetic, dielectric and phonon properties

Cited by 57 publications

References 40 publications

Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)

Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)

Nitrogen and fluorine co-doped graphene as a high-performance anode material for lithium-ion batteries

Giant ferrimagnetism and polarization in a mixed metal perovskite metal-organic framework

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Temperature-dependent studies of [(CH3)2NH2][FeIIIMII(HCOO)6] frameworks (MII = Fe and Mg): structural, magnetic, dielectric and phonon properties

Cited by 57 publications

References 40 publications

Synthesis and characterization of novel niccolites [(CH3)2NH2][FeIIIMII(HCOO)6] (MII= Zn, Ni, Cu)

Synthesis and characterization of novel niccolites [(CH3)2NH2][FeIIIMII(HCOO)6] (MII= Zn, Ni, Cu)

Nitrogen and fluorine co-doped graphene as a high-performance anode material for lithium-ion batteries

Giant ferrimagnetism and polarization in a mixed metal perovskite metal-organic framework

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Temperature-dependent studies of [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] frameworks (M^II = Fe and Mg): structural, magnetic, dielectric and phonon properties

Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)

Synthesis and characterization of novel niccolites [(CH₃)₂NH₂][Fe^IIIM^II(HCOO)₆] (M^II= Zn, Ni, Cu)