CH<sub>3</sub>CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure

Enjalbert, R.; Galy, Jean

doi:10.1107/s0108768102017603

Cited by 62 publications

(89 citation statements)

References 6 publications

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“…Furthermore, favorable N-H interactions between molecules in different rows (with N-H distances of 2.52Å and 2.80Å) further stabilize the all-parallel structure. The all-parallel monolayer resembles to some extent the low-temperature (β) phase of solid acetonitrile [38]. From these monolayer calculations we can conclude that acetonitrile matches the structure of the anatase(101) surface very well.…”

Section: Dftmentioning

confidence: 58%

See 1 more Smart Citation

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Schiffmann¹,

Hutter²,

VandeVondele³

2008

J. Phys.: Condens. Matter

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Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface Schiffmann, F; Hutter, J; VandeVondele, J Schiffmann, F;Hutter, J; VandeVondele, J (2008). Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface. Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface AbstractThe acetonitrile/anatase(101) interface can be considered a prototypical interface between an oxide and a polar aprotic liquid, and is common in dye sensitized solar cells. Using first principles molecular dynamics simulations of a slab of TiO2 in contact with neat acetonitrile (MeCN), the liquid structure near this interface has been characterized. Furthermore, in order to investigate properties that require extensive sampling, a classical force field to describe the MeCN/TiO2 interaction has been optimized, and we show that this force field accurately describes the structure near the interface. We find a surprisingly strong interaction of MeCN with TiO2, which leads to an ordered first MeCN layer displaying a significantly enhanced molecular dipole. The strong dipolar interactions between solvent molecules lead to pronounced layering further away from the interface, each successive layer having an alternate orientation of the molecular dipoles. At least seven distinct solvent layers (approximately 12 angstrom) can be discerned in the orientational distribution function. The observed structure also strongly suppresses diffusion parallel to the interface in the first nanometer of the liquid. These results show that the properties of the liquid near the interface differ from those in the bulk, which suggests that solvation near the interface will be distinctly different from solvation in the bulk.Atomistic simulations of a solid/liquid interface: A combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface Abstract.The acetonitrile / anatase(101) interface can be considered a prototypical interface between an oxide and a polar aprotic liquid, and is common in dye sensitized solar cells. Using first principles molecular dynamics simulations of a slab of TiO 2 in contact with neat acetonitrile (MeCN), the liquid structure near this interface has been characterized. Furthermore, in order to investigate properties that require extensive sampling, a classical force field to describe the MeCN/TiO 2 interaction has been optimized, and we show that this force field accurately describes the structure near the interface. We find a surprisingly strong interaction of MeCN with TiO 2 , which leads to an ordered first MeCN layer displaying a significantly enhanced molecular dipole. The strong dipolar interactions between solvent molecules lead to pronounc...

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Section: Dftmentioning

confidence: 58%

“…Such antiparallel dimers are also found in the high-temperature (α) phase of solid acetonitrile. [38] The corrugation of the surface is visible in the first solvent and second second layer.…”

Section: Solvent Structure Near the Interfacementioning

confidence: 98%

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Schiffmann¹,

Hutter²,

VandeVondele³

2008

J. Phys.: Condens. Matter

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“…2). [65][66][67][68][69][70][71][72] The low temperature (β or II) and high temperature (α or I) phases both consist of ordered AN molecules. 69 The solid-solid phase transition corresponds to a 90…”

Section: Resultsmentioning

confidence: 99%

Electrolyte Solvation and Ionic Association

Han

Borodin

Seo

et al. 2014

J. Electrochem. Soc.

116

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Electrolytes with the salt lithium bis(fluorosulfonyl)imide (LiFSI) have been evaluated relative to comparable electrolytes with other lithium salts. Acetonitrile (AN) has been used as a model electrolyte solvent due to the simplicity of its solvation interactions (the AN molecule has only a single electron lone-pair for Li + cation coordination). The information obtained from the thermal phase behavior, solvation/ionic association interactions, quantum chemical (QC) calculations and molecular dynamics (MD) simulations (with an APPLE&P many-body polarizable force field for the LiFSI salt) of the (AN) n -LiFSI mixtures provides detailed insight into the coordination interactions of the FSI − anions and the wide variability noted in the electrolyte transport properties (i.e., viscosity and ionic conductivity). was first reported in a patent application in 1995 which indicated a method for its synthesis.1 Its use in research studies, however, has been restricted until quite recently due to the limited availability and high cost of this salt. A limited number of publications have been reported about the use of the FSI − anion for electrolytes in recent years, 2-55 but many of these have focused on FSI − -based ionic liquids instead of the LiFSI salt. Recent papers, however, indicate that battery electrolytes with LiFSI have very promising properties-i.e., a relatively high thermal and hydrolytic stability (relative to LiPF 6 ), a high conductivity (comparable to electrolytes with LiPF 6 ) and a wide liquidus range. 2-18One key concern originated from reports which indicated that the use of the LiFSI salt in electrolytes results in severe corrosion of the battery Al current collector at high potentials. 3,15 It has recently been demonstrated, however, that this was likely due to chloride impurities in the salt (from the synthesis procedures) rather than the LiFSI salt itself. 12To fully capitalize upon the use of LiFSI as an alternative lithium salt for advanced lithium batteries, it is necessary to understand the behavior of this salt in bulk electrolyte solutions. The preceding work in this series of publications has scrutinized the relationship between the solution structure and transport properties of electrolytes in detail. 56-59The present study extends this focus to acetonitrile-based (AN) n -LiFSI electrolytes to better understand the characteristics of this relatively * Electrochemical Society Student Member.* * Electrochemical Society Active Member. z E-mail: Wesley.Henderson@pnnl.gov; oleg.a.borodin.civ@mail.mil new electrolyte salt. Of particular interest are the recent reports which noted that highly concentrated (AN) n -LiTFSI and -FSI electrolytes have a high electrochemical stability to reduction at negative potentials (in sharp contrast to more dilute solutions with nitrile solvents) which allows for the rapid and reversible charging/discharging of graphitic electrodes. 5,60 ExperimentalMaterials.-Anhydrous AN (Sigma-Aldrich, 99.8%) and LiFSI (Suzhou Fluolyte Co., Ltd., >99.5%) were used as-received....

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“…For example, Natile and coworkers reported that the addition of alcohols to coordinated nitriles to form iminoether complexes of Pt II takes place under basic conditions and that the iminoether ligand initially formed in the Z configuration and subsequently isomerized to the E configuration. [21] Although the Re I acetonitrile complexes we used have a low oxidation state, we discovered that, after the treatment of [Re(CO) 3 [9] are similar to those of the free acetonitrile molecule (1.145 Å) [24] and of the acetonitrile that is coordinated in the fac-{Re(CO) 3 } phosphane complexes. [25,26] However, these phosphane compounds have not been reported to form iminoether compounds, and such coordinated nitriles are not very reactive.…”

Section: Synthesismentioning

confidence: 96%

Iminoether Complexes of the Type, fac‐[Re(CO)₃L{HNC(CH₃)OCH₃}]BF₄ (L = Bipyridine or a Substituted Bipyridine): Synthesis and Properties

et al. 2012

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The methyl acetimidate (an iminoether) complexes, fac‐[Re(CO)3L{HNC(CH3)OCH3}]BF4 [where L = 2,2′‐bipyridine (bipy), 4,4′‐Me2bipy, 5,5′‐Me2bipy, or 6,6′‐Me2bipy], were formed when fac‐[Re(CO)3(CH3CN)3]BF4 in acetonitrile/methanol was treated with 2,2′‐bipyridine (bipy) or the dimethyl‐2,2′‐bipyridines (4,4′‐Me2bipy, 5,5′‐Me2bipy, or 6,6′‐Me2bipy). Structural analysis of the four fac‐[Re(CO)3L{HNC(CH3)OCH3}]BF4 complexes revealed that all of the complexes crystallize with the iminoether ligand in the Z configuration and that distortions in L that involved the two pyridyl rings are minor except for 6,6′‐Me2bipy, which is highly distorted. This distortion of the 6,6′‐Me2bipy ligand is reflected in the NMR‐spectroscopic data. Upon complex formation, the methyl group signal in the 13C NMR spectrum shifted downfield significantly for 6,6′‐Me2bipy, but this did not occur in the 13C NMR spectrum of the 5,5′‐Me2bipy complex. The reaction times for forming the respective fac‐[Re(CO)3L{HNC(CH3)OCH3}]BF4 complexes for these two ligands were comparable, which indicated that the differences in the distortion of L and the methyl substituent position have little influence on the ease of iminoether formation. However, a higher steric bulk of the alcohol (methanol, ethanol, and2‐propanol) decreases the ease of fac‐[Re(CO)3(5,5′‐Me2bipy){HNC(CH3)OR}]BF4 formation. Isopropanol did not form the iminoether complex after two days of heating the reaction mixture at reflux. The low reactivity of the alcohols tested versus the amines that were tested previously suggests that selective bioconjugation to the fac‐{99mTc(CO)3}+ core through an amidine linkage is feasible for biomolecules that have both amine and hydroxy groups. Finally, a comparison of the C≡N bond lengths that were obtained for the fac‐[Re(CO)3(CH3CN)3]BF4/PF6 complexes with those values obtained for other rhenium acetonitrile complexes revealed that there is no significant difference between the C≡N bond lengths and that there is no correlation to the acetonitrile reactivity. It is possible that the fac‐{Re(CO)3}+ core stabilizes the transition state for amine or alcohol addition.

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CH₃CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure

Cited by 62 publications

References 6 publications

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Electrolyte Solvation and Ionic Association

Iminoether Complexes of the Type, fac‐[Re(CO)₃L{HNC(CH₃)OCH₃}]BF₄ (L = Bipyridine or a Substituted Bipyridine): Synthesis and Properties

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CH3CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure

Cited by 62 publications

References 6 publications

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Atomistic simulations of a solid/liquid interface: a combined force field and first principles approach to the structure and dynamics of acetonitrile near an anatase surface

Electrolyte Solvation and Ionic Association

Iminoether Complexes of the Type, fac‐[Re(CO)3L{HNC(CH3)OCH3}]BF4 (L = Bipyridine or a Substituted Bipyridine): Synthesis and Properties

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Product

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CH₃CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure

Iminoether Complexes of the Type, fac‐[Re(CO)₃L{HNC(CH₃)OCH₃}]BF₄ (L = Bipyridine or a Substituted Bipyridine): Synthesis and Properties