Ionic Conductivities Induced by the Partial Solvent Molecule Removal from Diruthenium(II,III) Adamantanecarboxylate Salts

Na ß“-alumina (Na1.67Mg67Al10.33O17) is a non-stoichiometric sodium aluminate which exhibits fast ionic conduction of the Na+ ions in two dimensions. The Na+ ions can be exchanged with a variety of mono-, di-, and trivalent cations. The resulting exchanged materials also show high ionic conductivities.Considerable interest in the Na+-Nd3+-ß“-aluminas has been generated as a result of the recent observation of lasing in the pulsed and cw modes. A recent TEM investigation on a 100% exchanged Nd ß“-alumina sample found evidence for the intergrowth of two different structure types. Microdiffraction revealed an ordered phase coexisting with an apparently disordered phase, in which the cations are completely randomized in two dimensions. If an order-disorder transition is present then the cooling rates would be expected to affect the microstructures of these materials which may in turn affect the optical properties. The purpose of this work was to investigate the affect of thermal treatments upon the micro-structural and optical properties of these materials.

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A Crystallographic Study of Bis[S-benzyl-5-bromo-2-oxoindolin-3-ylidenemethanehydrazonthioate] Disulfide Solvated with Dimethylsulfoxide

Scientific Research Journal ◽

10.24191/srj.v9i2.9410 ◽

2012 ◽

Vol 9 (2) ◽

pp. 87

Author(s):

Mohd Abdul Fatah Abdul Manan ◽

M. Ibrahim M. Tahir ◽

Karen A. Crouse ◽

Fiona N.-F. How ◽

David J. Watkin

Keyword(s):

Crystal Structure ◽

Hydrogen Bonds ◽

Solvent Molecule ◽

Site Occupancy ◽

Unit Cell Parameters ◽

Intermolecular Hydrogen Bonds ◽

Triclinic Space Group ◽

Cell Parameters ◽

Crystallographic Study ◽

Thiol Form

The crystal structure of the title compound has been determined. The compound crystallized in the triclinic space group P -1, Z = 2, V = 1839 .42( 18) A3 and unit cell parameters a= 11. 0460( 6) A, b = 13 .3180(7) A, c=13. 7321 (8) A, a = 80.659(3 )0, b = 69 .800(3 )0 and g = 77 .007 (2)0 with one disordered dimethylsulfoxide solvent molecule with the sulfur and oxygen atoms are distributed over two sites; S101/S102 [site occupancy factors: 0.6035/0.3965] and 0130/0131 [site occupancy factor 0.3965/0.6035]. The C22-S2 l and C 19-S20 bond distances of 1. 779(7) A and 1. 788(8) A indicate that both of the molecules are connected by the disulfide bond [S20-S21 2.055(2) A] in its thiol form. The crystal structure reveals that both of the 5-bromoisatin moieties are trans with respect to the [S21-S20 and CI 9-Nl 8] and [S20-S21 and C22-N23] bonds whereas the benzyl group from the dithiocarbazate are in the cis configuration with respect to [S21-S20 and C19-S44] and [S20-S21 and C22-S36] bonds. The crystal structure is further stabilized by intermolecular hydrogen bonds of N9-H35···O16 formed between the two molecules and N28-H281 ···O130, N28-H281 ···O131 and C4 l-H4 l l ···O 131 with the solvent molecule.

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How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

10.26434/chemrxiv.11316497.v2 ◽

2020 ◽

Author(s):

Saneyuki Ohno ◽

Tim Bernges ◽

Johannes Buchheim ◽

Marc Duchardt ◽

Anna-Katharina Hatz ◽

...

Keyword(s):

Standard Deviation ◽

Ionic Conductivity ◽

Relative Standard Deviation ◽

Solid Electrolytes ◽

Ionic Conductivities ◽

Ionic Conductors ◽

Energy Storage Devices ◽

Activation Barriers ◽

Storage Devices ◽

Relative Standard

Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an interlaboratory reproducibility of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm-1 in the measured total ionic conductivity (1.3 – 5.8 mScm-1 for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.

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Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li6PS5Br

10.26434/chemrxiv.9794588 ◽

2019 ◽

Author(s):

Ajay Gautam ◽

Marcel Sadowski ◽

Nils Prinz ◽

Henrik Eickhoff ◽

Nicolo Minafra ◽

...

Keyword(s):

Elevated Temperatures ◽

Synthesis Method ◽

Reaction Times ◽

Ionic Conductivities ◽

Ionic Transport ◽

High Energy ◽

Superionic Conductors ◽

Rapid Crystallization ◽

Site Disorder ◽

Fast Cooling

Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li6PS5X (X = Cl, Br, I), a site-disorder between the anionsS2–and X–has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such disorder in Li6PS5Br can be engineered viathe synthesis method. By comparing fast cooling (i.e. quenching) to more slowly cooled samples, we find that anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with ab-initiomolecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within one minute of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced viaquenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.

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Can the Lewis basicity of an isolated solvent molecule be used for characterizing solvent effects?

Current Analytical Chemistry ◽

10.2174/1573411016999200607171803 ◽

2020 ◽

Vol 16 ◽

Author(s):

Jean-François Gal ◽

Pierre-Charles Maria

Keyword(s):

Solvent Effects ◽

Molecular Level ◽

Solvent Molecule ◽

Lewis Base ◽

Bulk Liquid ◽

Donor Number ◽

Special Focus ◽

Solution Processes ◽

Inert Solvent

Background: The ubiquitous Lewis acid/base interactions are important in solution processes. Analytical chemistry may benefit of a better understanding of the role of Lewis basicity, at the molecular level or acting through a bulk solvent effect. Objective: To clearly delineate (i) the basicity at a molecular level, hereafter referred as solute basicity, and (ii) the solvent basicity, which is a bulk-liquid property. Method: The literature that relates Lewis basicity scales and solvent effects is analyzed. A special focus is placed on two extensive scales, the Donor Number, DN, and the BF3 affinity scale, BF3A, which were obtained by calorimetric measurement on molecules as solutes diluted in a quasi-inert solvent, and therefore define a molecular Lewis basicity. We discuss the validity of these solute scales when regarded as solvent scales, in particular when the basicity of strongly associated liquids is discussed. Results: We demonstrate the drawbacks of confusing the Lewis basicity of a solvent molecule, isolated as solute, and that of the bulk liquid solvent itself. Conclusion: Consequently, we recommend a reasoned use of the concept of Lewis basicity taking clearly into account the specificity of the process for which a Lewis basicity effect may be invoked. In particular, the action of the Lewis base, either as an isolated entity, or as a bulk liquid, must be distinguished.

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Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19800406 ◽

1980 ◽

Vol 45 (2) ◽

pp. 406-414 ◽

Cited By ~ 4

Author(s):

Jiří Svoboda ◽

Oldřich Paleta ◽

Václav Dědek

Keyword(s):

Reaction Mechanism ◽

Proton Transfer ◽

Substituent Effect ◽

Solvent Molecule ◽

Addition Product ◽

Potassium Fluoride ◽

Relative Reactivity ◽

Addition Reactions ◽

Tertiary Amines ◽

Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

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Radical Intermediates in Photochemical and Redox Initiated Decomposition of Thioazo Compounds(an EPR and Cyclovoltammetric Study)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19970855 ◽

1997 ◽

Vol 62 (6) ◽

pp. 855-865 ◽

Cited By ~ 3

Author(s):

Katarína Erentová ◽

Vladimír Adamčík ◽

Andrej Staško ◽

Oskar Nuyken ◽

Arming Lang ◽

...

Keyword(s):

Decomposition Rate ◽

Half Life ◽

Spin Trap ◽

Solvent Molecule ◽

Life Time ◽

Radical Intermediates ◽

Reactive Radicals ◽

Induced Decomposition

The cathodically and photochemically induced decomposition of thioazo compounds XC6H4-N2-S-C6H4CH3 and their polymers with X = NO2, COOH, and SO3H were investigated. The formation of carbon-centered XC6H4. and sulfur-centered .S-C6H4Y radicals was confirmed using spin-trap technique. These reactive radicals either abstract hydrogen from CH3CN solvent molecule forming .CH2CN radical or they recombine to cage products XC6H4-S-C6H4CH3 eliminating N2. The decomposition rate of the investigated thioazo compounds is characterized by a formal half-life time of 5 to 10 s.

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Gas-Phase Clustering of NO+ with H2S and H2O

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20071122 ◽

2007 ◽

Vol 72 (8) ◽

pp. 1122-1138 ◽

Cited By ~ 2

Author(s):

Milan Uhlár ◽

Ivan Černušák

Keyword(s):

Hydrogen Bonds ◽

Water Molecule ◽

Gas Phase ◽

Saddle Points ◽

Solvent Molecule ◽

Local Minima ◽

Additional Water ◽

Three Body ◽

Rain Formation ◽

Stable Structures

The complex NO+·H2S, which is assumed to be an intermediate in acid rain formation, exhibits thermodynamic stability of ∆Hº300 = -76 kJ mol-1, or ∆Gº300 = -47 kJ mol-1. Its further transformation via H-transfer is associated with rather high barriers. One of the conceivable routes to lower the energy of the transition state is the action of additional solvent molecule(s) that can mediate proton transfer. We have studied several NO+·H2S structures with one or two additional water molecule(s) and have found stable structures (local minima), intermediates and saddle points for the three-body NO+·H2S·H2O and four-body NO+·H2S·(H2O)2 clusters. The hydrogen bonds network in the four-body cluster plays a crucial role in its conversion to thionitrous acid.

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Solid Polymer Electrolytes from Crosslinked PEG and Dilithium N,N'-Bis(trifluoromethanesulfonyl)perfluoroalkane-1,ω-disulfonamide and Lithium Bis(trifluoromethanesulfonyl)imide Salts

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20081777 ◽

2008 ◽

Vol 73 (12) ◽

pp. 1777-1798 ◽

Cited By ~ 1

Author(s):

Olt E. Geiculescu ◽

Rama V. Rajagopal ◽

Emilia C. Mladin ◽

Stephen E. Creager ◽

Darryl D. Desmarteau

Keyword(s):

Ionic Conductivity ◽

Polymer Electrolytes ◽

Minimum Energy ◽

Ionic Conductivities ◽

Solid Polymer Electrolytes ◽

Solid Polymer ◽

Segmental Motion ◽

Concentrated Electrolytes ◽

Two Factors ◽

Poly Ethylene

The present work consists of a series of studies with regard to the structure and charge transport in solid polymer electrolytes (SPE) prepared using various new bis(trifluoromethanesulfonyl)imide (TFSI)-based dianionic dilithium salts in crosslinked low-molecular-weight poly(ethylene glycol). Some of the thermal properties (glass transition temperature, differential molar heat capacity) and ionic conductivities were determined for both diluted (EO/Li = 30:1) and concentrated (EO/Li = 10:1) SPEs. Trends in ionic conductivity of the new SPEs with respect to anion structure revealed that while for the dilute electrolytes ionic conductivity is generally rising with increased length of the perfluoroalkylene linking group in the dianions, for the concentrated electrolytes the trend is reversed with respect to dianion length. This behavior could be the result of a combination of two factors: on one hand a decrease in dianion basicity that results in diminished ion pairing and an enhancement in the number of charge carriers with increasing fluorine anion content, thereby increasing ionic conductivity while on the other hand the increasing anion size and concentration produce an increase in the friction/entanglements of the polymeric segments which lowers even more the reduced segmental motion of the crosslinked polymer and decrease the dianion contribution to the overall ionic conductivity. DFT modeling of the same TFSI-based dianionic dilithium salts reveals that the reason for the trend observed is due to the variation in ion dissociation enthalpy, derived from minimum-energy structures, with respect to perfluoroalkylene chain length.

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Hydride-based antiperovskites with soft anionic sublattices as fast alkali ionic conductors

Nature Communications ◽

10.1038/s41467-020-20370-2 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Shenghan Gao ◽

Thibault Broux ◽

Susumu Fujii ◽

Cédric Tassel ◽

Kentaro Yamamoto ◽

...

Keyword(s):

Experimental Studies ◽

Ionic Conductivities ◽

Cubic Phase ◽

Ionic Conductors ◽

Large Size ◽

Migration Barriers ◽

Soft Phonon Mode ◽

Aliovalent Substitution ◽

Cubic Forms ◽

The Ideal

AbstractMost solid-state materials are composed of p-block anions, only in recent years the introduction of hydride anions (1s2) in oxides (e.g., SrVO2H, BaTi(O,H)3) has allowed the discovery of various interesting properties. Here we exploit the large polarizability of hydride anions (H–) together with chalcogenide (Ch2–) anions to construct a family of antiperovskites with soft anionic sublattices. The M3HCh antiperovskites (M = Li, Na) adopt the ideal cubic structure except orthorhombic Na3HS, despite the large variation in sizes of M and Ch. This unconventional robustness of cubic phase mainly originates from the large size-flexibility of the H– anion. Theoretical and experimental studies reveal low migration barriers for Li+/Na+ transport and high ionic conductivity, possibly promoted by a soft phonon mode associated with the rotational motion of HM6 octahedra in their cubic forms. Aliovalent substitution to create vacancies has further enhanced ionic conductivities of this series of antiperovskites, resulting in Na2.9H(Se0.9I0.1) achieving a high conductivity of ~1 × 10–4 S/cm (100 °C).

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