Stable Cation Research Articles

Stable Radical Cation and Dication of a 1,4-Disilabenzene.

The reaction of (LSi:)2 (1; L = PhC(NtBu)2) with 2 equiv of Me3SiC2C2SiMe3 resulted in the formation of (Me3SiC2)2(Me3Si)2C4Si2(L)2 (2). 2 exhibited a one-electron transfer when treated with 1 equiv of [Ph3C]+[B(C6F5)4]- to yield [(Me3SiC2)2(Me3Si)2C4Si2(L)2]·+[B(C6F5)4]- (3) and Ph3CCPh3, respectively. When compound 2 was treated with 2 equiv of AgOSO2CF3 a transfer of two electrons occurred to produce [(Me3SiC2)2(Me3Si)2C4Si2(L)2]2+·2[OSO2CF3]- (4) and elemental silver. The 1,4-disilabenzene 2 is disclosed of an open-shell singlet diradical character, and 3 and 4 are, respectively, the elusive stable radical cation and dication species of the 1,4-disilabenzene (2). Furthermore, 2 reacted with group 16 elements of O, S, and Se by oxidative addition to form (Me3SiC2)2(Me3Si)2C4Si2(L)2(μ-O2) (5) and (Me3SiC2)2(Me3Si)2C4Si2(L)2(μ-E) (E = S (6) and Se (7)), respectively.

Influence of isomeric phthaloperinone monomers on the formation of π-dimers and σ-bonded segments in electrochemically-crosslinked products

A mixture of three constitutional isomers containing terminal reactive phthaloperinone units was obtained by the condensation of 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) with 1,8-naphthalenediamine. Both terminal units underwent an addition reaction via electrochemical oxidation and subsequent reduction at the perimidine core and isoindolinone, respectively, to create a multi-directional crosslinked product. The course of electropolymerization depended significantly on the isomer used, which was related to the intermediate products formed during electrooxidation: π-dimers formed in the precursor solution with stronger π-π interactions between radical cations and/or products containing π-conjugated segments: bis-isoindolinone, bis-perimidine (bonded via 3/4 and 3′/4′ positions) and protonated σ-bonded bis-perimidine via 1/6 and 1′/3′/4′/6′ positions, where hydrogen bonds stabilized these latter adducts and prevented their deprotonation. The polymers were characterized by a mixed structure, which had different effects on the long-range interactions, stability of hydrogen bonds providing a redox center located on the protonated dicationic bis-perimidine segment underwent reversible reduction to stable radical cation.

Intramolecular Halo Stabilization of Silyl Cations-Silylated Halonium- and Bis-Halo-Substituted Siliconium Borates.

The stabilizing neighboring effect of halo substituents on silyl cations was tested for a series of peri‐halo substituted acenaphthyl‐based silyl cations 3. The chloro‐ (3 b), bromo‐ (3 c), and iodo‐ (3 d) stabilized cations were synthesized by the Corey protocol. Structural and NMR spectroscopic investigations for cations 3 b–d supported by the results of density functional calculations, which indicate their halonium ion nature. According to the fluorobenzonitrile (FBN) method, the silyl Lewis acidity decreases along the series of halonium ions 3, the fluoronium ion 3 a being a very strong and the iodonium ion 3 d a moderate Lewis acid. Halonium ions 3 b and 3 c react with starting silanes in a substituent redistribution reaction and form siliconium ions 4 b and 4 c. The structure of siliconium borate 4 c 2[B12Br12] reveals the trigonal bipyramidal coordination environment of the silicon atom with the two bromo substituents in the apical positions.

Modelling interactions of cationic dimers in He droplets: microsolvation trends in HenK2+ clusters.

We report the results of a detailed theoretical investigation of small K2+-doped He clusters. The structural characteristics and stabilities of such cations are determined from ab initio electronic structure calculations at the MRCI+Q level of theory. The underlying interactions show a multireference character and such effects are analyzed. The interaction potentials are constructed employing an interpolation technique within the inverse problem theory method, while the nuclear quantum effects are computed for the trimers, their spatial arrangements are discussed, and information was extracted on the orientational anisotropy of the forces. We found that energetically the most stable conformer corresponds to linear arrangements that are taking place under large amplitude vibrations, with high zero-point energy. We have further looked into the behavior of higher-order species with various He atoms surrounding the cationic dopant. By using a sum of potentials approach and an evolutionary programming method, we analyzed the structural stability of clusters with up to six He atoms in comparison with interactions energies obtained from MRCI+Q quantum chemistry computations. Structures containing Hen motifs that characterize pure rare gas clusters, appear for the larger K2+-doped He clusters, showing selective growth during the microsolvation process of the alkali-dimer cation surrounded by He atoms. Such results indicate the existence of local solvation microstructures in these aggregates, where the cationic impurity could get trapped for a short time, contributing to the slow ionic mobility observed experimentally in ultra-cold He-droplets.

Patterning microporous paper with highly conductive silver nanoparticles via PVP-modified silver–organic complex ink for development of electric valves

The stabilization of silver cations generated from silver-reactive ink by PVP on HEC-modified Whatman No. 1 paper and enhanced electrowetting properties for developing a paper-based microfluidic device equipped with an electrical valve.

Electron doping of single-walled carbon nanotubes using pyridine-boryl radicals.

Pyridine-boryl (py-boryl) radicals serve as efficient electron-doping reagents for single-walled carbon nanotubes (SWCNTs). The doping mechanism comprises electron transfer from the py-boryl radical to the SWCNT. The formation of a stable py-boryl cation is essential for efficient doping; the captodative effect of the py-boryl cation is important to this process.

Half-sandwich manganese complexes Cp(CO)2Mn(NHC) as redox-active organometallic fragments.

Oxidation of the half-sandwich MnI complexes Cp(CO)2Mn(NHC) bearing dialkyl-, arylalkyl- and diarylsubstituted N-heterocyclic carbene ligands (NHC = IMe, IMeMes, IMes) affords the corresponding stable MnII radical cations [Cp(CO)2Mn(NHC)](BF4) isolated in 92-95% yield. Systematic X-ray diffraction studies of the series of MnI and MnII NHC complexes revealed the expected characteristic structural changes upon oxidation, namely the elongation of the Mn-CO and Mn-NHC bonds as well as the diminution of the OC-Mn-CO angle. ESR spectra of [Cp(CO)2Mn(IMes)](BF4) in frozen solution (CH2Cl2/toluene 1 : 1, 70 K) allowed the identification of two conformers for this complex and their structural assignment using DFT calculations. The stability of these NHC complexes in both metal oxidation states, moderate oxidation potentials and the ease of detection of MnII species by a variety of spectroscopic techniques (UV-Vis, IR, paramagnetic 1H NMR, and ESR) make these compounds promising objects for applications as redox-active organometallic fragments.

Aryl carbazole-based macrocycles: synthesis, their remarkably stable radical cations and host–guest complexation with fullerenes

Herein, we have designed and synthesized a series of aryl carbazole-based macrocycles and their stable radical cation species and interesting fullerene recognition were systematically investigated.

Local structure and NO adsorption/desorption property of Pd2+ cations at different paired Al sites in CHA zeolite.

Recently, Pd-exchanged CHA zeolites (Pd-CHA) have attracted attention as promising passive NOx adsorbers (PNAs) for reducing NOx emissions during the cold start period of a vehicle engine. In this work, the relationship between the local structures and the NO adsorption/desorption properties of the Pd cations in CHA zeolites was investigated. Pd cation formation and NO adsorption were theoretically explored by density functional theory (DFT) calculations for different paired Al sites in six-/eight-membered rings (6MR/8MR). Furthermore, we prepared a series of Pd-CHAs with different Pd loadings (0.5-5.4 wt%) and evaluated their NO adsorption/desorption properties by in situ infrared (IR) spectroscopy and temperature-programmed desorption (TPD) measurements. The increase in the Pd loading resulted in a shift in the NO desorption temperature toward a higher temperature regime. This phenomenon was ascribed to the increase in the proportion of less stable Pd cations, resulting in improved NO adsorption. Furthermore, the effect of Al distribution on the NO adsorption property of Pd-CHA was examined using CHA zeolites containing different proportions of paired Al sites in 6MR while maintaining similar Si/Al ratios (Si/Al = 12.0-16.5). The present study, based on a combination of theoretical and experimental techniques, shows that the NO adsorption/desorption properties over Pd-CHA can be tuned by controlling the Pd loading amount and the type of paired Al sites.

Ir-Ni based mono and bimetallic nanocrystals: synthesis, characterization and effect of cationic, anionic, and non-ionic stabilizers

Nickel based bimetallic nanocrystals, iridium-nickel play an imperative role in catalysis, electrocatalysis, and magnetic applications. In the present work Ir-Ni bimetallic nanoalloys were synthesized by modified polyol reduction method with different cationic, anionic, and non-ionic surface active agents like CTAB, SDS, TSC, and PVP. The non-ionic surface active agent PVP produced a better effect on nanoparticle size than cationic and anionic surfactants. The synthesized bimetallic nanocrystals were characterized by UV-Vis, XRD, FTIR, FESEM, and HRTEM techniques. XRD and FTIR verify the nature of synthesized bimetallic nanocrystals and the interaction between stabilizers and nanoparticles. HRTEM studies reveal that the PVP stabilized Ir-Ni (3:1) and Ir-Ni (1:1) bimetallic nanocrystals are small in size and less dispersed. Particle size range of these nanoparticles is from (1.77-2.36) nm. FESEM images show that nanoparticles are in quasi spherical shape. EDX analysis indicates that the resultant particles are core shell structure with Ni core and Ir shell.

Grape pectic polysaccharides stabilization of anthocyanins red colour: Mechanistic insights

Grape pectic polysaccharides-malvidin-3-O- β -d-glucoside binding was studied, aiming to unveil the impact of structural diversity of polysaccharides on anthocyanins-polysaccharides interactions. Polysaccharides were extracted with solutions of imidazole (ISP) and carbonate at 4 °C (CSP-4 °C) and room temperature (CSP-RT) and also recovered from the dialysis supernatant of the remaining cellulosic residue after the aqueous NAOH extraction of hemicellulosic polysaccharides (Sn-CR). Polysaccharides richer in homogalacturonan domains, like those present in the CSP-4 °C fraction had approximately 50–fold higher binding affinity to malvidin-3-O- β-d-glucoside, than polysaccharides with side chains (as ISP and CSP-RT extractable polysaccharides). CSP-4 °C polysaccharides showed a positive effect on malvidin-3-O- β-d-glucoside colour fading. Hydration equilibrium constant of malvidin-3-O- β-d-glucoside in the presence of CSP-4 °C polysaccharides was higher, showing the preferential stabilization of the flavylium cation. The results showed that anthocyanins colour stabilization can be promoted by pectic polysaccharide structures such as those extracted by cold carbonate.

Thermally, Electrochemically, and Mechanically Tough Polymer Electrolytes Containing a Solvate Ionic Liquid for Lithium Secondary Battery

Lithium-ion rechargeable batteries (LIB) are energy storage devices with extremely high energy density, which play an essential role in portable electronic devices as well as electric vehicles. Conventional LIBs are composed of Li-intercalated cathode materials, graphite anode, and liquid electrolytes prepared by dissolving Li salts into organic solvents. Recently, a gel electrolyte, i.e., a three-dimensional polymer network swollen by a liquid electrolyte, is commercially used to bestow flexibility in the battery design, which contributes to the development of thin electronic devices. However, these gel materials are volatile, and their mechanical reliabilities are low.In the last few decades, high-voltage cathode materials with over 4 V of operating voltage such as LiCoO2 (LCO, capacities of ca. 140 mA h g−1) and LiNi1/3Mn1/3Co1/3O2 (NMC111, capacities of ca. 150 mA h g−1) have been applied to lithium-ion batteries. Recently, next-generation cathode materials with a higher capacity and operating voltage, such as Ni-rich NMC, LiNi0.6Mn0.2Co0.2O2 (NMC622, capacities of ca. 180 mA h g−1 for 4.4 V of cut-off voltage) have been proposed for the higher capacity. The dramatic increase of the energy density of LIB contributes to the development of long-life portable electronic devices, however at the same time, causes a safety issue (i.e., short circuit, overheating, and explosion) due to the flammability of organic solvents. Most of the conventional gel electrolytes prepared by soaking a polymer network into an organic liquid electrolyte. Thus, the improvement of the thermal stability and mechanical property of the gel electrolytes is one of the critical issues.In this study, to overcome these problems of gel electrolytes, we developed thermally, electrochemically stable, and mechanically tough electrolyte using a solvate ionic liquid (SIL) and a homogeneous polymer network. SIL, which is prepared by mixing equimolar glyme (oligoether, Gn, n = 3, 4) and a lithium salt, is known as a new class of ionic liquids (ILs). Triglyme (G3) or tetraglyme (G4) and Li cation form a stable cation complex ([Li(G3)]+ or [Li(G4)]+) by chelating solvation of O atoms toward Li cation, resulting in non-flammability, good thermal and electrochemical stability analogous to ILs as well as Li-ion conductivity. Herein, we used a equimolar mixture of G4 and lithium bis(trifluoromethanesulfonyl)amide ([Li(G4)][TFSA]). On the other hand, as a homogeneous network, we employed 4-armed poly(ethylene glycol) (TetraPEG) network with excellent mechanical property due to homogeneous dispersion of stress when they are deformed.However, mixing polymers with high polarity including PEG with SIL results in deterioration of thermal and electrochemical stabilities of SIL. This is due to the interaction of electron-rich PEG chains with Li cation, which disrupts [Li(G4)]+ complex, resulting in generation of free G4, which is volatile and easily oxidative. To improve this, we prepared lithium-solvated tetraPEG (LS-TPEG) with ratio of O atoms to Li cation, [O]/[Li] = 5, which corresponds to that of [Li(G4)]+ complex. LS-TPEG/[Li(G4)][TFSA] showed high thermal and electrochemical stabilities comparable to [Li(G4)][TFSA] as well as good ionic conductivity (~ 1 mS cm−1 at 25 °C). The gel electrolyte also showed excellent mechanical properties inherent in homogeneous polymer network, including stretchability (>100%). We investigated the charge/discharge behavior of Li | gel electrolyte | NMC622, which showed a stable charge/discharge. The enhancement of thermal, electrochemical, and mechanical stabilities of the gel electrolyte was accomplished in the aspect of homogeneity of polymer network and solvation structures of polymer and solvent.

Implication of aliovalent cation substitution on structural and thermodynamic stability of Gd2Ti2O7: Experimental and theoretical investigations

Multi-cation substituted pyrochlores are potential matrices for immobilization of long-lived high level nuclear waste. In this paper, we report, the structural and thermodynamic stabilities of aliovalent multi cation substituted Gd2Ti2O7 pyrochlore compounds determined by experimental and theoretical methods. A series of cubic pyrochlore-type Gd2-2xCaxZrxTi2O7 (0.0 ≤ x ≤ 0.4) compounds were synthesized and characterized by XRD and Raman spectroscopy techniques. It is observed that incorporation of Ca2+ and Zr4+ at Gd3+ site does not significantly alter crystal lattice of Gd2Ti2O7. Calorimetric studies were carried out to determine the thermodynamic stability of Gd2-2xCaxZrxTi2O7 compounds. The observed data indicate that standard molar enthalpy of formation of Gd2-2xCaxZrxTi2O7 decreases steadily with increasing dopant concentration which has been attributed to increasing distortion of the polyhedra around the cations. These inferences were further supported by DFT calculations.

Selective Hydrolysis of Terminal Glycosidic Bond in α-1-Acid Glycoprotein Promoted by Keggin and Wells-Dawson Type Heteropolyacids.

The reactivity of a range of Keggin and Wells-Dawson type heteropolyacids (HPAs): H3 PW12 O40 H4 SiW12 O40 , H3 PMo12 O40 , K6 P2 W18 O62 , and NaH2 W12 O4 , towards the heavily glycosylated α-1-acid glycoprotein (AGP) is reported. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) show that after incubation of the protein with HPAs at 80 °C and pH 2.8 complete hydrolysis of terminal glycosidic bond has been achieved, resulting in the removal of sialic acids with no observed destruction of the protein core or the residual glycan chains. The 1 H NMR spectroscopy confirmed that the released sialic acids preserve intact structure upon their excision from the protein, which makes the reported method suitable for the analysis of sialic acid modifications which play an important role in numerous biological processes. The presence of other sugars was not detected by 1 H NMR and HPAEC-PAD, suggesting that HPAs hydrolyze only the terminal glycosidic bond in the glycoprotein, resulting in the selective release of sialic acid from AGP. The kinetic results have shown that under equal temperature and pH conditions, the hydrolysis of the terminal glucosidic bond occurred faster in the presence of HPAs compared to conventional mineral acids. The observed rate constants were in the range 6,7×10-2 -11,9×10-2 min-1 and the complete and selective excision of sialic acids could be achieved within 60 min of incubation. The Trp fluorescence and CD spectroscopy show that non-covalent interaction between HPA and protein takes place in solution which could lead to stabilization of the sialosyl cation that is formed during the glycosidic bond hydrolysis by anionic HPA cluster.

Fluoride shuttle batteries: On the performance of the BiF3 electrode in organic liquid electrolytes containing a mixture of lithium bis(oxalato)borate and triphenylboroxin

In a typical organic liquid electrolyte-based fluoride shuttle battery (FSB), a high concentration of a boron-based anion acceptor (AA) capable of binding specific anions is required to provide a sufficient amount of dissolved fluoride salt. In this study, and a mixture of lithium bis(oxalato)borate (LiBOB) and an AA, triphenylboroxin (TPhBX), was used as an organic liquid electrolyte. The tetraglyme (G4)-based electrolyte system (LiBOB0.25/TPhBX0.25/sat_CsF/G4) containing equal concentrations of LiBOB, TPhBX, and saturated cesium fluoride (CsF) was prepared. The potential effects of reducing the amount of the AA and using a mixture of LiBOB and TPhBX on the electrochemical compatibility of the BiF3 electrode were investigated through cyclic voltammetry, charge–discharge tests, and alternating current impedance measurements. The potential advantages of using the LiBOB/TPhBX mixture as an electrolyte additive include the fact that it increases ionic conductivity, widens the cathodic and anodic stability window, and enhances the electrochemical performance of the BiF3 positive electrode. Moreover, according to Raman microscopy, the direct insertion mechanism was found to be predominant for the FSB reaction mechanism of BiF3 microparticles in LiBOB0.25/TPhBX 0.25/sat_CsF/G4. These improvements can be attributed to the increase in fluorine anion mobility, which occurs when the cesium cation mobility is reduced; this, in turn, is a result of the stabilization of the cesium cation due to the interaction between LiBOB and TPhBX. Therefore, mixing equal concentrations of LiBOB and TPhBX can be a promising alternative method to ensure electrolyte stability and prevent the potential loss of active materials during the redox reactions.

Solvation of potential stable cations and anions originating from the Martian regolith in select ionic liquids

Element recovery from the Martian regolith using ionic liquids (ILs) is an active area of research within the field of in-situ resource utilization. In this work, we performed a classical molecular dynamics (MD) simulation study to better understand the solvation thermodynamics and structures of potential cationic and anionic species originating from the Martian regolith in two select ILs, i.e., 1-ethyl-3-methylimidazolium acetate ([emim][Ac]) and 1-ethyl-3-methylimidazolium hydrogen sulfate ([emim][HSO4]), at two temperatures of 298.15 and 473.15 K. The studied cationic and anionic species represent the stable ions, i.e., a series of tetra-, tri-, di-, and monovalent cations, as well as several silicate, phosphate, chromate, titanate, and select halide anions, based on the mineral composition of the Martian regolith. We calculated the solvation free energies (SFEs) of these ionic species in the ILs using the free energy perturbation method. Moreover, we investigated the solvation environment of these ionic solutes by generating the relevant radial distribution functions and calculating the running coordination numbers of ILs' anions and cations surrounding the solutes. Overall, the average absolute values of the SFEs for cationic solutes increase with increasing ion valency (charge) and size of the solute at both temperatures. For anionic solutes, a more complex effect of anion molecular size and charge is responsible for the trends observed in the absolute values of the SFEs. For example, we found orthosilicate to be the most soluble anionic species in both ILs. On the other hand, the dichromate anion was found to be essentially insoluble in both ILs. Comparing between the solvation efficiencies of the ILs, [emim][Ac] shows larger negative SFE values than [emim][HSO4] for all cationic solutes at both temperatures. While the temperature effect on the solvation of cationic solutes is mixed, higher temperatures generally favor the dissolution of the anionic solutes in both ILs. Our results provide molecular insights into the solvation thermodynamics of various potential ionic species that may be extracted from the Martian regolith using suitable ILs.

Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

AbstractWe show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous RhI complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh1/CeO2 achieve full NO conversion with a turn‐over‐frequency (TOF) of around 330 h−1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2O being the minor product. The presence of water promotes low‐temperature activity of 0.1 wt % Rh1/CeO2. In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH3 formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.

Economizing on Precious Metals in Three-Way Catalysts: Thermally Stable and Highly Active Single-Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions*.

We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high-temperature atom-trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous RhI complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh1 /CeO2 achieve full NO conversion with a turn-over-frequency (TOF) of around 330 h-1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2 O being the minor product. The presence of water promotes low-temperature activity of 0.1 wt % Rh1 /CeO2 . In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH3 formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.

On the stability and chemical bond of noble gas halide cations NgX+ (Ng = He - Rn; X = F - I).

Despite the belief that noble gases (Ng) are completely inert and cannot form stable molecules, a variety of Ng compounds have been reported under laboratory conditions and others were recently detected in the interstellar media, raising interest in knowing and studying their bond nature and the physicochemical properties associated with their stability. In the present work, a systematic analysis of the thermodynamic stability of noble gas halide cations (NgX+ ) at the CCSD(T)/def2-QZVP level have been performed. In addition, chemical bond was characterized through Natural Bonding Theory (NBO), Quantum Theory of Atoms in Molecules (QTAIM) and Energy Decomposition Analysis (EDA) with relativistic corrections. All methods suggest that NgX+ compounds possess a strong covalent bond. However, results show that only compounds containing Ar-Rn atoms are thermodynamic stable with a highly energetic and endergonic dissociation process. For these reasons, it is possible to suggest that several compounds that have not yet been reported could be obtained at the laboratory level or observed in the interstellar medium.

Ion Solvation Engineering: How to Manipulate the Multiplicity of the Coordination Environment of Multivalent Ions.

Free energy analysis of solvation structures of free divalent cations, their ion pairs, and neutral aggregates in low dielectric solvents reveals the multiplicity of thermodynamically stable cation solvation configurations and identifies the micro- and macroscopic factors responsible for this phenomenon. Specifically, we show the role of ion-solvent interactions and solvent mixtures in determining the cation solvation free energy landscapes. We show that it is the entropic contribution of solvent degrees of freedom that is responsible for the solvation multiplicity, and the mutual balance between enthalpic and entropic forces or their concerted contributions is what ultimately defines the most stable ion solvation configuration and creates new ones. We show general consequences of ion solvation multiplicity on thermodynamics of complex electrolytes, specifically in the context of homogeneous or interfacial charge transfer. Identified factors and their interplay provide a pathway to formulation of solvation design rules that can be used to control bulk solvation, interfacial chemistry, and charge transfer. Our findings also suggest experimentally testable predictions.