Manifestation of interionic interactions in the ir absorption spectra of the tetrafluoroborate ion

Perelygin, I. S.; Klimchuk, M. A.

doi:10.1007/bf00659987

Cited by 7 publications

(7 citation statements)

References 6 publications

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“…Despite the extensive attention devoted to the probe of ion−molecule and ion−ion interactions in solutions using vibrational spectroscopy, only very limited spectroscopic studies − were performed on the association of LiBF 4 . Alía and Edwards 11 studied the Raman spectra of LiBF 4 in acrylonitrile and found the presence of contact ion pairs and their dimers.…”

Section: Introductionmentioning

confidence: 99%

Vibrational Spectroscopic and Density Functional Studies on Ion Solvation and Association of Lithium Tetrafluorobrate in Acetonitrile

et al. 2004

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Vibrational spectroscopic studies have been carried out on solutions of LiBF 4 in acetonitrile as a function of concentrations of lithium salt. Great changes in the vibrational characteristics of CtN and C-C stretches were observed as a result of solvation. The solvation numbers of Li + determined from spectroscopic data are found to decrease from 3.2 to 1.4 with increasing concentration of the lithium salt. It is expected that the solvation number is 4 in the infinite diluted solution. Solvation structures of the lithium ion were suggested by density functional theory and the results were compared with the spectroscopic data. Changes of the ν 1 mode of BF 4 -with concentration of the salt were also analyzed, and the bands at 763, 771, and 780 cm -1 indicate the coexisting of free ion, contact ion pairs, and dimers. The structures of ion pairs in gas phase and in acetonitrile solutions were suggested on the basis of DFT calculations.

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Section: Introductionmentioning

confidence: 99%

Vibrational Spectroscopic and Density Functional Studies on Ion Solvation and Association of Lithium Tetrafluorobrate in Acetonitrile

et al. 2004

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“…Signatures of ion pairing in solutions are seen, first of all, as extra lines appearing in the vicinity of intense lines corresponding to non-degenerated vibrations of anions. Upon adding LiBF 4 to DMSO, the 1 line of BF − 4 splits into three components at 760, 763, and 768 cm −1 , which can be assigned to anions in the free state, in SSIPs, and in CIPs, respectively [25,46,47]. The integrated intensities of the component lines vary with the salt concentration.…”

Section: Resultsmentioning

confidence: 99%

Picosecond Dynamics of Molecular Entities in Lithium Salt Solutions in Dimethyl Sulfoxide, Propylene Carbonate, and Dimethyl Carbonate

Gorobets

Kirillov

2018

Ukr. J. Phys.

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An analysis of the Raman spectra of the solutions of lithium salts in dimethyl sulfoxide, propylene carbonate, and dimethyl carbonate in a concentration range from diluted solutions to the mixtures of molten solvates with salts has been performed in terms of the dynamics, specifically, the dephasing (тv) and modulation (тw) times of all molecular entities present in solutions are determined and analyzed. It has been found that, in the picosecond time domain, the dephasing and modulation in solvent molecules hydrogen-bonded with an anion and/or solvating a cation are slower than in free solvent molecules. In solvent separated ion pairs, both тv and тw are much longer than in solvated anions, thus indicating the strong interactions between anions and their surrounding. In contact ion pairs, тv are great, whereas тw appear close to those for free anions. This reflects that the structure of the liquid tends to the structure of molten salts.

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“…The incorporation of hydrogen-bonding water molecules was also observed using infrared spectroscopy (Supporting Information); on standing in air, the carbon–nitrogen triple bond stretching frequency from lattice acetonitrile molecules at 2249 cm –1 in 4 is lost, and a new broad peak emerges at ∼3600 cm –1 . The prominent absorbance at 1047 cm –1 originating from the tetrafluoroborate anions also displays slight broadening upon exposure of 4 to air, consistent with the desymmetrization and addition of hydrogen-bond acceptor character to these groups …”

Section: Results and Discussionmentioning

confidence: 99%

“…The prominent absorbance at 1047 cm −1 originating from the tetrafluoroborate anions also displays slight broadening upon exposure of 4 to air, consistent with the desymmetrization and addition of hydrogen-bond acceptor character to these groups. 23 In order to probe the solvent exchange and structural rearrangement process further, the lattice acetonitrile molecules in a freshly prepared sample of 4 were exchanged for 1,4dioxane, a low-volatility solvent incapable of participating in the hydrogen-bonding interactions that are thought to have caused the pore collapse in 5. Exchange of the lattice acetonitrile molecules was achieved by soaking the freshly prepared compound 4, without allowing the crystals to dry, in 1,4dioxane (20 mL/50 mg).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Coordination Chemistry and Structural Dynamics of a Long and Flexible Piperazine-Derived Ligand

et al. 2016

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A long and highly flexible internally functionalized dipyridyl ligand α,α'-p-xylylenebis(1-(4-pyridylmethylene)-piper-4-azine), L, has been employed in the synthesis of a series of coordination polymer materials with Co(II), Cd(II), and Ag(I) ions. In poly-[Cd(L)(TPA)] 1 and poly-[Co(L)(IPA)], 2, (TPA = terephthalate, IPA = isophthalate) the ligand adopts a similar linear conformation to that seen in the structure of the unbound molecule and provides a long (2.6 nm) metal-metal bridging distance. Due to the mismatch of edge lengths with that provided by the carboxylate coligands, geometric distortions from the regular dia and (4,4) network geometries for 1 and 2, respectively, are observed. In poly-[Ag2(CF3SO3)2(L)], 3, the ligand coordinates through both pyridine groups and two of the four piperazine nitrogen donors, forming a high-connectivity 2-dimensional network. The compound poly-[Ag2(L)](BF4)2·2MeCN, 4, a porous 3-dimensional cds network, undergoes a fascinating and rapid single-crystal-to-single-crystal rearrangement on exchange of the acetonitrile guests for water in ambient air, forming a nonporous hydrated network poly-[Ag2(L)](BF4)2·2H2O, 5, in which the well-ordered guest water molecules mediate the rearrangement of the tetrafluoroborate anions and the framework itself through hydrogen bonding. The dynamics of the system are examined in greater detail through the preparation of a kinetic product, the dioxane-solvated species poly-[Ag2(L)](BF4)2·2C4H8O2, 6, which undergoes a slow conversion to 5 over the course of approximately 16 h, a transition which can be monitored in real time. The reverse transformation can also be observed on immersing the hydrate 5 in dioxane. The structural features and physical properties of each of the materials can be rationalized based on the flexible and multifunctional nature of the ligand molecule, as well as the coordination behavior of the chosen metal ions.

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Manifestation of interionic interactions in the ir absorption spectra of the tetrafluoroborate ion

Cited by 7 publications

References 6 publications

Vibrational Spectroscopic and Density Functional Studies on Ion Solvation and Association of Lithium Tetrafluorobrate in Acetonitrile

Vibrational Spectroscopic and Density Functional Studies on Ion Solvation and Association of Lithium Tetrafluorobrate in Acetonitrile

Picosecond Dynamics of Molecular Entities in Lithium Salt Solutions in Dimethyl Sulfoxide, Propylene Carbonate, and Dimethyl Carbonate

Coordination Chemistry and Structural Dynamics of a Long and Flexible Piperazine-Derived Ligand

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