Growth and characterization of potassium cobalt nickel sulfate hexahydrate crystals: A new UV light filter

Pacheco, Tiago S.; Ghosh, Santunu; Oliveira, Michelle de; Barbosa, Ananias A.; Perpétuo, Genivaldo Júlio; Franco, Carlos J.

doi:10.1016/j.jsamd.2017.08.002

Cited by 15 publications

(9 citation statements)

References 21 publications

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“…In fact, it is frequently the case that papers reporting vibrational spectra of metal salt hydrates do not include figures showing the ν(OH) region even when they do include figures showing other regions of IR and/or Raman spectra. In most cases this is understandable, because, as Figure S17 shows, the ν(OH) region in room temperature IR spectra of salt hydrates typically does not contain precise, meaningful information. ,,− …”

Section: Resultsmentioning

confidence: 99%

“…We are studying anhydrous, hydrated, solvated, and ligated metal ion salts of the icosahedral superweak anion B 12 F 12 2– (hereinafter Z 2– ). − The structures and other properties of M(H 2 O) n (Z) hydrates can serve as models for the hydration of alkaline earth and transition metal ions in solution − or in extended solids such as clays, − zeolites, , or metal–organic frameworks (MOFs). − The degree of hydration of an alkaline earth or transition metal compound can affect its electrical or proton conductivity, − its photoluminescence intensity, its fluorescence red-shift, or its ability to act as a UV filter, − among other physicochemical properties. The dehydration/rehydration behavior of M(H 2 O) n (Z) salts is especially important in light of the interest in thermodynamic and kinetic dehydration/rehydration studies of salt hydrates for the storage of low potential heat from solar energy. − Some salt hydrates are known to change their structure when D 2 O replaces H 2 O .…”

Section: Introductionmentioning

confidence: 99%

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Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

et al. 2018

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Eight M(H2O) n (Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z2– = B12F12 2–): M = Ca, Sr, n = 7; M = Mg, Co, Ni, Zn, n = 6; M = Ba, n = 4, 5. Weak O–H···F hydrogen bonding between the M(H2O) n 2+ cations and Z2– resulted in room-temperature Fourier transform infrared (FTIR) spectra having sharp ν(OH) bands, with full widths at half max of 10–30 cm–1, which are much more narrow than ν(OH) bands in room temperature FTIR spectra of most salt hydrates. Clearly resolved νasym(OH/OD) and νsym(OH/OD) bands with Δν(OH) as small as 17 cm–1 and Δν(OD) as small as 11 cm–1 were observed (Δν(OX) = νasym(OX) – νsym(OX)). The isomorphic hexahydrates (R3̅) have two fac-(H2O)3 sets of H2O ligands and nearly octahedral coordination spheres. They exhibited four resolvable ν(OH) bands, one νasym(OH)/νsym(OH) pair for H2O ligands with longer O(H)···F distances and one νasym(OH)/νsym(OH) pair for H2O ligands with shorter O(H)···F distances. The ν(OH) bands for the three H2O molecules with shorter, slightly stronger O(H)···F hydrogen bonds were broader, more intense, and red-shifted by ca. 25 cm–1 relative to the bands for the three other H2O molecules, the first time that such small differences in relatively weak O(H)···F hydrogen bonds in the same crystalline hexahydrate have resulted in observable IR spectroscopic differences at room temperature. For the first time room temperature ν(OH) values for salt hexahydrates showed the monotonic progression Mg2+ > Co2+ > Ni2+ > Zn2+, essentially the same progression as the pK a values for these metal ions in aqueous solution. A further manifestation of the weak O–H···F hydrogen bonding in these hydrates is the latent porosity exhibited by Ba(H2O)5,8(Z), Sr(H2O) n,m (Z), and Ca(H2O)4,6(Z). Finally, the H2O/D2O exchange reaction Co(D2O)6(Z) → Co(H2O)6(Z) was ca. 50% complete in 1 h at 50 °C in N2/17 Torr H2O(g).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

et al. 2018

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“…Also, they can be used as radiation filters in UV/IR detectors used for military purposes in missile approach warning systems. 3,5,6 The structure of Tutton salt is composed of SO connections can be affected by agents such as dopants/ impurities in the crystalline network of these materials. The presence of dopants can lead to changes in the normal vibrational modes of the molecular groups SO 4 , NH 4 , H 2 O, and M(H 2 O) 6 .…”

Section: Introductionmentioning

confidence: 99%

“…Tutton salt crystals started to be studied by Alfred E. H. Tutton around 1890. − This family of isostructural crystals can assume a broad range of compositions with different properties. Interestingly, regardless of their chemical composition, this family of salts crystallizes in the monoclinic system with the spatial group P 2 1 / c with two molecules occupying the unit cell Z = 2.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

et al. 2023

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In this work, we synthesized and studied the spectroscopic properties of (NH 4 ) 2 (SO 4 ) 2 Y(H 2 O) 6 (Y = Ni, Mg) crystals doped with AgNO 3 or H 3 BO 3 . These crystals constitute a series of hexahydrated salts known as Tutton salts. We investigated the influence of dopants on the vibrational modes of the tetrahedral ligands NH 4 and SO 4 , octahedral complexes Mg(H 2 O) 6 and Ni(H 2 O) 6 , and H 2 O molecules present in these crystals through Raman and infrared spectroscopies. We were able to identify bands that are attributed to the presence of Ag and B dopants, as well as band shifts caused by the presence of these dopants in the crystal lattice. A detailed study of the crystal degradation processes was performed by thermogravimetric measurements, where there was an increase in the initial temperature of crystal degradation due to the presence of dopants in the crystal lattice. Raman spectroscopy of the crystal residues after the thermogravimetric measurements helped us to elucidate the degradation processes occurring after the crystal pyrolysis process.

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“…Tutton salts form a hexahydrate isomorphic crystallographic family with a general chemical formula M 2 M*(XO 4 ) 2 •6H 2 O, where M is occupied by a monocation (Cs + , K + , Rb + , Tl + , and NH 4 + ), M* represents a dication (Mg 2+ , V 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ Cd 2+ ), and X is a site constituted by S or Se atoms [15,16]. These salts crystallize in a monoclinic system with P2 1 /a space group containing two formulas per unit cell (Z = 2) [17].…”

Section: Introductionmentioning

confidence: 99%

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

et al. 2022

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Tutton salts have been extensively explored in recent decades due to their attractive physical and chemical properties, which make them potential candidates for thermochemical heat storage systems and optical technologies. In this paper, a series of new mixed Tutton salts with the chemical formula (NH4)2Mn1–xZnx(SO4)2(H2O)6 is reported. Crystals are successfully grown by the solvent slow evaporation method and characterized by powder X-ray diffraction (PXRD) with Rietveld refinement. In particular, the crystal structure of the mixed (NH4)2Mn0.5Zn0.5(SO4)2(H2O)6 crystal is solved through PRXD data using the DICVOL06 algorithm for diffraction pattern indexing and the Le Bail method for lattice parameter and spatial group determination. The structure is refined using the Rietveld method implemented in TOPAS® and reported in the Cambridge Structural Database file number 2104098. Moreover, a computational study using Hirshfeld surface and crystal void analyses is conducted to identify and quantify the intermolecular interactions in the crystal structure as well as to determine the amount of free space in the unit cell. Furthermore, 2D-fingerprint plots are generated to evaluate the main intermolecular contacts that stabilize the crystal lattice. Density functional theory is employed to calculate the structural, thermodynamic, and electronic properties of the coordination [Zn(H2O)6]2+ and [Mn(H2O)6]2+ complexes present in the salts. Molecular orbitals, bond lengths, and the Jahn–Teller effect are also discussed. The findings suggest that in Mn-Zn salts several properties dependent on the electronic structure can be tuned up by modifying the chemical composition.

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Growth and characterization of potassium cobalt nickel sulfate hexahydrate crystals: A new UV light filter

Cited by 15 publications

References 21 publications

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

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Growth and characterization of potassium cobalt nickel sulfate hexahydrate crystals: A new UV light filter

Cited by 15 publications

References 21 publications

Manifestations of Weak O–H···F Hydrogen Bonding in M(H2O)n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H2O)n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO3 or H3BO3

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

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Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO₃ or H₃BO₃