IR spectra and microstructure of electrolyte solutions. Dependence of spectroscopic characteristics of solvated molecules on composition of solvates in the system CH3CN–Mg(ClO4)2–DMF

Akopyan, S. Kh.; Bertagnolli, Helmut; Boyarskaya, Irina А.; Leicht, Daniel; Merkle, Rotraut; Solovieva, L.A.; Vilaseca, Eudald

doi:10.1039/b101742j

Cited by 10 publications

(2 citation statements)

References 2 publications

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“…The same M-O bond lengths have also been found in [Mg(DMF) 6 ] ClO 4 2 and [Mg(DMA) 6 ] ClO 4 2 crystals. 57 Some theoretical approaches to the solvation structure of the magnesium and zinc ions have been reported for water 35,58,59 and AN, 60 but not for DMF and DMA so far. 49,50 IR and/or Raman spectroscopic studies on the solvation of the alkaline earth metal ions in DMF have been carried out, 51 -56 and preferential solvation of the magnesium ion has been studied in acetonitrile (AN)-DMF mixtures.…”

Section: Introductionmentioning

confidence: 99%

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Asada

Fujimori

Fujii

et al. 2006

J Raman Spectroscopy

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The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ , respectively, in both DMF and DMA. The d (O-C-N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift 1n .= n bound − n free / becomes larger, when the ionic radius of the metal ion becomes smaller. The n (N-CH 3 ) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift 1n saturates for small ions, as well as the transition-metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six-coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent-solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift 1n in DMF-DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large.the calcium ion varies from 6 to 10 depending on its concentration. 9,11,14,20 -29 The hydration structure has also been studied by theoretical calculations. [30][31][32][33] have studied hydrated clusters of magnesium and alkaline earth metal ions in the gas phase using an electrospray ionization (ESI) technique combined with high-pressure mass spectroscopy and revealed that the hydration enthalpies of these metal ions are in excellent agreement with those theoretically obtained. 35 The zero-pressure-limit dissociation rate for the loss of a single water molecule from the hydrated clusters of the magnesium and the alkaline earth metal ions has also been studied in the gas phase. 36

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Section: Introductionmentioning

confidence: 99%

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Asada

Fujimori

Fujii

et al. 2006

J Raman Spectroscopy

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“…In ternary mixtures of DMF + inorganic salt + nitrile group containing organics (acetonitrile,13 acrylonitrile,14 or PAN15), it has been reported that DMF has higher affinity (or preferentially solvates) toward cations from inorganic salts than nitrile compounds in the mixture. However, the change in solvation power of DMF caused by its complexation with salts has not been measured.…”

Section: Introductionmentioning

confidence: 99%

Poly(acrylonitrile) ultrafiltration membranes. I. Polymer‐salt‐solvent interactions

Phadke

Musale

Kulkarni

et al. 2005

J Polym Sci B Polym Phys

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Fourier transform infrared spectroscopy was used to study the interactions among LiCl, ZnCl2, and AlCl3 with N,N‐dimethylformamide (DMF) and poly(acrylonitrile) (PAN). It was observed that all three salts complex with DMF as well as PAN. The strength of the cation interaction with the >CO oxygen of DMF was found to be higher than that with the CN group of PAN. The >CO stretching frequency of DMF with ZnCl2 was red shifted, indicating stronger complex formation compared with other two cations. With the addition of salt, the salt–DMF pseudo solvent was found to become a θ solvent for PAN compared with neat DMF. This change in PAN solvation power was primarily the result of DMF–salt complexation. As a result of the complexation, Mark‐Houwink constant a, was found to reduce from 0.75 (for pure DMF) to ∼0.6 for DMF–salt solvents, indicating decreased PAN chain expansion. Comparison of intrinsic viscosity [η] values indicated that addition of salts to PAN–DMF solutions resulted in: (i) decrease in the DMF solvation power, which causes less expanded polymer coils, and (ii) increased interpolymer chain entanglements via salt‐promoted chain association. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2061–2073, 2005

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IR Spectra and DFT Calculations of M–η²‐(NC)–CH₃, CH₃–MNC, and CH₂=M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Acetonitrile

Cho

Andrews

2015

Eur J Inorg Chem

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Keywords: Matrix isolation / IR spectroscopy / Hafnium / Titanium / Density functional calculations Laser-ablated Hf and Ti atoms produce M-η 2 -(NC)-CH 3 , CH 3 -MNC, and CH 2 =M(H)NC in reactions with acetonitrile, parallel to the earlier Zr results, based on isotopic substitution and frequencies computed by DFT. These products are the most stable components in the previously proposed reaction path for reactions of metal atoms with acetonitrile, in line with the observed products in other metal systems and DFT calculations. Other plausible products

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IR spectra and microstructure of electrolyte solutions. Dependence of spectroscopic characteristics of solvated molecules on composition of solvates in the system CH3CN–Mg(ClO4)2–DMF

Cited by 10 publications

References 2 publications

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Poly(acrylonitrile) ultrafiltration membranes. I. Polymer‐salt‐solvent interactions

IR Spectra and DFT Calculations of M–η²‐(NC)–CH₃, CH₃–MNC, and CH₂=M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Acetonitrile

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IR spectra and microstructure of electrolyte solutions. Dependence of spectroscopic characteristics of solvated molecules on composition of solvates in the system CH3CN–Mg(ClO4)2–DMF

Cited by 10 publications

References 2 publications

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Solvation structure of magnesium, zinc, and alkaline earth metal ions in N,N‐dimethylformamide, N,N‐dimethylacetamide, and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

Poly(acrylonitrile) ultrafiltration membranes. I. Polymer‐salt‐solvent interactions

IR Spectra and DFT Calculations of ­M–η2‐(NC)–CH3, CH3–MNC, and CH2=M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Aceto­nitrile

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IR Spectra and DFT Calculations of M–η²‐(NC)–CH₃, CH₃–MNC, and CH₂=M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Acetonitrile