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The nonheme iron(IV)-oxido complex trans-N3-[(L1)FeIV=O(Cl)]+, where L1 is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, has an S = 1 electronic ground state and is the most reactive nonheme iron model system known so far, of a similar order of reactivity as nonheme iron enzymes (C-H abstraction of cyclohexane, 90 °C (propionitrile), t1/2 = 3.5 sec). The reaction with cyclohexane selectively leads to chlorocyclohexane, but “cage escape” at the [(L1)FeIII-OH(Cl)]+ / cyclohexyl radical intermediate lowers the productivity. Ligand field theory is used herein to analyze the d-d transitions of [(L1)FeIV=O(X)]n+ (X = Cl, Br, MeCN) in comparison with the thoroughly characterized ferryl complex of tetramethylcyclam (TMC=L2; [(L2)FeIV=O(MeCN)]2+). The ligand field parameters and d-d transition energies are shown to provide important information on the triplet-quintet gap and its correlation with oxidation reactivity.

3,5-Diiodo-8-aryl-BODIPYs are prepared from the corresponding 3,5-dichloro- and 3,5-dibromo- congeners via a double aromatic Finkelstein reaction with NaI in refluxing propionitrile, in yields from 51 to 100%. Rate enhancement is observed for 3,5-dibromo-BODIPYs (ArBr > ArCl) suggesting a concerted SNAr mechanism for this transformation. Thus formed 3,5-diiodo-BODIPYs are examined as coupling partners in Migita-Kosugi-Stille, Mizoroki-Heck, Sonogashira, and Suzuki-Miyaura reactions, providing routes toward complex BODIPY architectures.

The nonheme iron(IV)‐oxido complex trans‐N3‐[(L1)FeIV=O(Cl)]+, where L1 is a derivative of the tetradentate bispidine 2,4‐di(pyridine‐2‐yl)‐3,7‐diazabicyclo[3.3.1]nonane‐1‐one, is known to have an S=1 electronic ground state and to be an extremely reactive oxidant for oxygen atom transfer (OAT) and hydrogen atom abstraction (HAA) processes. Here we show that, in spite of this ferryl oxidant having the “wrong” spin ground state, it is the most reactive nonheme iron model system known so far and of a similar order of reactivity as nonheme iron enzymes (C−H abstraction of cyclohexane, −90 °C (propionitrile), t 1/2=3.5 sec). Discussed are spectroscopic and kinetic data, supported by a DFT‐based theoretical analysis, which indicate that substrate oxidation is significantly faster than self‐decay processes due to an intramolecular demethylation pathway and formation of an oxido‐bridged diiron(III) intermediate. It is also shown that the iron(III)‐chlorido‐hydroxido/cyclohexyl radical intermediate, resulting from C−H abstraction, selectively produces chlorocyclohexane in a rebound process. However, the life‐time of the intermediate is so long that other reaction channels (known as cage escape) become important, and much of the C−H abstraction therefore is unproductive. In bulk reactions at ambient temperature and at longer time scales, there is formation of significant amounts of oxidation product – selectively of chlorocyclohexane – and it is shown that this originates from oxidation of the oxido‐bridged diiron(III) resting state., The nonheme iron(IV)‐oxido complextrans‐N3‐[(L1)FeIV=O(Cl)]+ is an extremely reactive oxidant for OAT and HAA processes and is the most reactive nonheme iron model system known so far and of similar reactivity as nonheme iron enzymes. Discussed are spectroscopic and kinetic data, supported by a DFT‐based theoretical analysis. In bulk reactions cyclohexane is selectively oxidized to chlorocyclohexane.

The electrical conductivity, density and diffusion coefficients of trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P66614][NTf2]) ionic liquid and its binary solutions in acetonitrile, propionitrile, dimethyl and diethyl carbonates were measured in the temperature range of 293 – 348 K. Electrical conductivity – ionic liquid mole fraction dependencies for the binary solutions were fitted with the empirical Casteel−Amis equation. The temperature dependencies of electrical conductivities were analyzed using the Arrhenius, Litovitz and Vogel-Fulcher-Tammann approaches. The activation energies and pre-exponential factor calculated using the Arrhenius equation for different mole fractions of ionic liquid were fitted with the empirical equations proposed in the literature. The thermo-gravimetric analysis combined with mass spectrometry demonstrated the high thermal stability of [P66614][NTf2] up to 600 K. At higher temperatures the decomposition of [P66614][NTf2] proceeds via the elimination of alkyl radicals as a result of the nucleophilic attack of reactive intermediates to [P66614]+ cation with the formation of trialkylphosphines. The activation energies of thermal destruction of [P66614][NTf2] were calculated using Kissinger equation and non-linear integral isoconversional model.

Adiponitrile (ADN) is an important raw material to produce nylon 66, and can be produced by electrodimerization of acrylonitrile (AN). The commercial processes are operated in flow systems. It is the first time that a rotating rod electrode (RRE), a relatively simple tool, was applied in the electrosynthesis of ADN. The electrode rotation rate was used to simulate high electrolyte velocity in the flow cell systems used in the industry. In addition to AN and ADN, the concentrations of two major by-products, propionitrile (PN) and trimer, were measured to determine the selectivity and current efficiency. Among five investigated quaternary ammonium salts in the electrolyte, tetrabutylammonium hydroxide (TBAP) possessing the smallest hydrophilic ability and hydrophilic-lipophilic balance (HLB) showed the best performance in the selectivity and current efficiency of ADN. A higher electrode rotation rate provided faster mass transport of AN and promoted the production of oligomers, particularly ADN. Higher current density favored the production of PN. The highest selectivity (85%), current efficiency (82%) and highest yield (0.331 g/cm2·hr) of adiponitrile were accomplished at 3000 rpm, corresponding to a velocity of 1.25 m/s in the range of the electrolyte flow velocity in commercial processes that other researches cannot easily reach it.

Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF4 )2 ⋅6 H2 O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz)2 (RCN)2 ](BF4 )2 ⋅nRCN (n=2 for R=CH3 (1) and n=0 for R=C2 H5 (2) C3 H7 (3), C3 H5 (4), CH2 Cl (5)) exhibiting spin crossover (SCO). SCO in 1 and 3-5 is complete and occurs above 160 K. In 2, it is shifted to lower temperatures and is accompanied by wide hysteresis (T1/2↓ =78 K, T1/2↑ =123 K) and proceeds extremely slowly. Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed a complex nature for the HS→LS transition in 2. An initial, slow stage is associated with shrinkage of polymeric chains and with reduction of volume at 77 % (in relation to the difference between cell volumes VHS -VLS ) whereas only 16 % of iron(II) ions change spin state. In the second stage, an abrupt SCO occurs, associated with breathing of the crystal lattice along the direction of the Fe-nitrile bonds, while the nitriles reorient. HS→LS switching triggered by light (808 nm) reveals the coupling of spin state and nitrile orientation. The importance of this coupling was confirmed by studies of [Fe(ebtz)2 (C2 H5 CN/C3 H7 CN)2 ](BF4 )2 mixed crystals (2 a, 2 b), showing a shift of T1/2 to higher values and narrowing of the hysteresis loop concomitant with an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Density functional theory (DFT) studies of models of 1-5 suggest a particular possibility of 2 to adopt a low (140-145°) value of its Fe-N-C(propionitrile) angle.

Electrochemical synthesis based on electrons as reagents provides a broad prospect for commodity chemical manufacturing. A direct one-step route for the electrooxidation of amino C-N bonds to nitrile C≡N bonds offers an alternative pathway for nitrile production. However, this route has not been fully explored with respect to either the chemical bond reforming process or the performance optimization. Proposed here is a model of vacancy-rich Ni(OH)2 atomic layers for studying the performance relationship with respect to structure. Theoretical calculations show the vacancy-induced local electropositive sites chemisorb the N atom with a lone pair of electrons and then attack the corresponding N(sp3 )-H, thus accelerating amino C-N bond activation for dehydrogenation directly into the C≡N bond. Vacancy-rich nanosheets exhibit up to 96.5 % propionitrile selectivity at a moderate potential of 1.38 V. These findings can lead to a new pathway for facilitating catalytic reactions in the chemicals industry.

Since 2015, during northern spring, a massive “noxious” stratospheric cloud has been detected at 250 km of altitude at the south pole of Titan, which persisted until the last targeted Cassini's flybys in July 2016. Its chemical composition seems to be the result of a co-condensation process of benzene and hydrogen cyanide in a 4:1 mixing ratio. Since, its altitude of detection allows to undergo long-UV solar radiations known to trigger photochemical aging processes, we experimentally simulated its evolution under stratospheric-like radiation conditions. The ice photo-processing (λ > 200 nm) led to the detection of nitriles by infrared spectroscopy such as acetonitrile (CH3CN), benzonitrile (C6H5CN) as well as a partial identification of propionitrile (CH3CH2CN) and acrylonitrile (C2H3CN). Gas chromatography coupled to mass spectrometry (GC–MS) analyses of the volatile fraction released in the gas phase during the warming of the photo-processed ice have been confirmed by previous assignments and provided the detection of several other hydrocarbons ranging from C3 to C8. These experimental results are of prime interest in the context of the future Dragonfly mission. They provide a list of nitrile derivatives that can be produced from this stratospheric cloud. Indeed, they may contribute at the end to the organic layer that recovers Titan's surface and would be analyzed by the mass spectrometer (Dra-MS) of this space mission.

International audience; Cocrystallization of 7,7′,8,8′-tetracyanoquinodimethane radical anion (TCNQ −•) and 3-methylpyridinium-1,2,3,5dithiadiazolyl radical cation (3-MepyDTDA +•) afforded isostructural acetonitrile (MeCN) or propionitrile (EtCN) solvates containing cofacial π dimers of homologous components. Loss of lattice solvent from the diamagnetic solvates above 366 K affords a high-temperature paramagnetic phase containing discrete TCNQ −• and weakly bound π dimers of 3-MepyDTDA +• , as evidenced by X-ray diffraction methods and magnetic susceptibility measurements. Below 268 K, a first-order phase transition occurs, leading to a low-temperature diamagnetic phase with TCNQ −• σ dimer and π dimers of 3-MepyDTDA +•. This study reveals the first example of cooperative interactions between two different organic radical ions leading to magnetic bistability, and these results are central to the future design of multicomponent functional molecular materials.

The Ritter-type amidation of cyclopropane-containing norbornane hydrocarbons proceeds via cyclopropane ring opening upon treatment with aceto- or propionitrile and water in the presence of FeCl3·6 H2O as a catalyst.

Three new niobium cluster compounds with edge bridged, octahedral hexanuclear metal cores have been synthesised. They consist of cluster pairs with [Nb6Cl12(RCN)6]2+ cations, [Nb6Cl18]2− anions, and co-crystallised nitrile molecules, with R = C2H5 (propionitrile), n C3H7 (butyronitrile), i C3H7 (isobutyronitrile). The synthesis is based on the dehydration of [Nb6Cl14(H2O)4] · 4(H2O) with carboxylic acid anhydrides in the presences of an excess of the respective nitrile. An interesting aspect of these compounds is that the metal atoms of the cluster cation have an average oxidation state different from that of the cluster anion, the former being oxidized losing two electrons. In crystals of all three compounds layers of cluster cations are separated by layers of cluster anions. Perpendicular to these layers of the same cluster types, every cation is surrounded by four anions and vice versa. Between the cations and anions short distances are found between the halogenido ligands and the positively charged C atoms of the nitrile ligands (N–C · · · Cl angles of ~90°). These contacts indicate relatively strong dipole-dipole interactions, which presumably contribute to the arrangement of the cluster ions in the crystals.

The structure and thermal expansion of the astronomical molecule propionitrile have been determined from 100 to 150 K using synchrotron powder X-ray diffraction. This temperature range correlates with the conditions of Titan's lower stratosphere, and near surface, where propionitrile is thought to accumulate and condense into pure and mixed-nitrile phases. Propionitrile was determined to crystallize in space group, Pnma (No. 62), with unit cell a = 7.56183 (16) Å, b = 6.59134 (14) Å, c = 7.23629 (14), volume = 360.675 (13) Å3 at 100 K. The thermal expansion was found to be highly anisotropic with an eightfold increase in expansion between the c and b axes. These data will prove crucial in the computational modelling of propionitrile–ice systems in outer Solar System environments, allowing us to simulate and assign vibrational peaks in the infrared spectra for future use in planetary astronomy.

The synthesis of propionitrilium derivatives of cobalt and iron bis(dicarbollides) [8-EtCN-3,3′-M(1,2-C2B9H10)(1′,2′-C2B9H11)] (M = Co, Fe) by the reaction of the cesium salts of the parent bis(dicarbollide) anions [3,3′-M(1,2-C2B9H11)2]− with propionitrile in the presence of tert-butyl bromide is described. The nucleophilic addition reactions of water, alcohols, and thiols with the –N+C triple bond of the prepared nitrilium derivatives were studied and the corresponding iminols [8-EtC(OH)HN-3,3′-M(1,2-C2B9H10)(1′,2′-C2B9H11)] (M = Co, Fe), imidates [8-EtC(OR)HN-3,3′-M(1,2-C2B9H10)(1′,2′-C2B9H11)] (M = Co, R = Me, Et, i-Pr, Bu; M = Fe, R = Et), and thioimidates [8-EtC(SR)HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] (R = Et, Bu, Hx) were synthesized as mixtures of E and Z-isomers, some of which could be separated by the column chromatography on silica. The molecular structure of [(Z)-8-EtC(OiPr)HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] was determined by single-crystal X-ray diffraction study.

The aim of this study was to find a solvent to replace N-methyl-2-pyrrolidone (NMP) in CO2 absorption systems containing the amine 2-amino-2-methyl-1-propanol (AMP), in order to reduce the health risks associated with handling, as NMP is reproductively toxic. Seven organic solvents were investigated: dimethyl sulfoxide (DMSO), 3-(dimethylamino)propionitrile (3DMAPN), 1-pentanol (1 P), propylene carbonate (PC), 4-heptanone (4 H), 1-methylimidazole (1MIMI) and cyclohexanol (CH). Henry’s constant, the CO2 solubility and the differential heat of absorption were determined for the pure solvents, and in solvent mixtures containing 25 wt% AMP, at 25 °C and 40 °C. Three of the solvents were found to have promising absorption properties: DMSO, 3DMAPN and 1 P. In mixtures with AMP, precipitation was formed at both 25 and 40 °C, and the CO2 absorption capacity was similar to that in the AMP–NMP system, in terms of the CO2 loading for a given partial pressure of CO2. The results also indicated that the reaction of AMP and CO2 in these solvents can be described by the zwitterion reaction mechanism.

Multinary organic-inorganic metal halide materials beyond the perovskite motif can help to address both fundamental aspects such as the electronic interactions between different metalate building units and practical issues like stability and ease of preparation in this new field of research. However, such multinary compounds have remained quite rare for the halogenido pentelates, as the formation of simpler side phases can be a significant hindrance. Here, we report a family of four new multinary iodido pentelates [PPh4]2[ECu2I7(nitrile)] (E = Sb, Bi; nitrile = acetonitile or propionitrile), including the first metalate with a Cu-I-Sb unit. The compounds can be obtained by facile solution or mechanochemical methods and display good stability up to 160 °C. A comparison with compounds containing binary anions [EI6]3- reveals that, unexpectedly, the addition of the iodido cuprate unit causes a blue-shift in the absorption of the antimonates but a red-shift in the bismuthates. Photoluminescence investigations at 10 K show that the compounds display broad luminescence bands that correspond well with the trend in their onset of absorption. Overall, the work highlights that multinary, non-perovskite halogenido metalates can be a valuable expansion of the chemistry of metal halide perovskites.

A facile and efficient acid-catalyzed cascade reaction for the synthesis of novel biheteroaryl structural motifs containing densely functionalized furans has been developed. The reaction sequence involves a Knoevenagel condensation of arylglyoxals with aroyl or heteroaroylacetonitrile and subsequently an isocyanide insertion via formal [4+1] cycloaddition followed by rapid [1,3]-H shift to afford uniquely decorated novel biheterocycles. Furthermore, the scope of the methodology was extended to diverse biheteroaryls by employing 3-(2-furyl)-3-oxopropanenitrile, 3-cyanoacetyl-1-methylindole, 3-oxo-3-(1H-pyrrol-2-yl)propanenitrile, 3-(1H-indol-3-yl)-3-oxopropanenitrile, 3-Oxo-3-(2-thienyl)propionitrile and benzoylacetonitriles.

Narejene so bile reakcije cinkovega(II) kinaldinata s piperidinom v propionitrilu ali benzonitrilu. Reakcije so bile narejene pri različnih pogojih: (i) v avtoklavih pri 105 °C, (ii) segrevanju ob pogojih refluksa, in (iii) na sobni temperaturi. Pri reakcijah v propionitrilu sem izolirala štiri produkte: [Zn(quin)2(pipe)]PrCN, [Zn(quin)2(pipe)2]PrCN, pipePrAmH[Zn(quin)3] ter produkt, ki najverjetneje vsebuje amidin. Natančna sestava slednjega še ni poznana. Pri reakcijah v benzonitrilu sem izolirala dva produkta: [Zn(quin)2(pipe)2]2,5PhCN in [Zn(quin)2(pipePhAm)]. Zinc(II) quinaldinate was reacted with piperidine in propionitrile or benzonitrile. Reactions were carried out at three different reaction conditions: (i) in autoclaves at 105 °C, (ii) by heating under reflux, and (iii) at ambient conditions. Reactions in propionitrile afforded four products: [Zn(quin)2(pipe)]PrCN, [Zn(quin)2(pipe)2]PrCN, pipePrAmH[Zn(quin)3] and a compound that most likely contains amidine. Its composition has not been confirmed so far. Reactions in benzonitrile afforded two products: [Zn(quin)2(pipe)2]2,5PhCN and [Zn(quin)2(pipePhAm)].

Crystals of [FeL2][BF4]2·nMeCN (L = N-(2,6-di{pyrazol-1-yl}pyrid-4-yl)acetamide; n = 1 or 2) and [FeL2][ClO4]2·MeCN are isomorphous. When n = 1 the compounds exhibit an abrupt, hysteretic spin-transition below 200 K, but when n = 2 the material remains high-spin on cooling. [FeL2]X2·EtCN (X− = BF4− or ClO4−) are isomorphous with the MeCN solvates and undergo their spin-transition at almost the same temperature. However this now occurs in two-steps via a re-entrant mixed-spin intermediate phase, which correlates with crystallographic ordering of the bent propionitrile molecule.

One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands.

Cyclopropanes are traditionally prepared by the formal [2+1] addition of carbene or radical based C1 units to alkenes. In contrast, the one pot intermolecular cyclopropanation of alkanes by redox active C1 units has remained unrealised. Herein, we achieved this process simply by exposing β‐aryl propionitriles and C1 radical precursors ( N ‐oxy esters) to base and blue light. The overall process is redox‐neutral and a photocatalyst, whether metal‐ or organic‐based, is not required. Our findings support that single electron transfer (SET) from the α‐cyano carbanion of the propionitrile to the N ‐oxy ester is facilitated by blue‐light via their electron donor‐acceptor (EDA) complex. The α‐cyano carbon radical thus formed can then lose a β‐proton to form a π‐resonance stabilised radical anion that preferentially couples at the benzylic β‐position with a decarboxylated C1 radical unit. This new transition metal‐free chemistry tolerates both electron rich and electron deficient (hetero)aryl systems, even sulfide or alkene functionality, to afford a range of cis ‐aryl/cyano cyclopropanes bearing congested tetrasubsitituted quaternary carbons.

Binding energies of different nitrile solvents and their utilization for CuCN formation were investigated through quantum chemical calculations. A pulsed laser ablation in liquid (PLAL) method for CuCN synthesis was developed herein. Initially, the interaction between the pulsed laser and the Cu-target generated Cu-ions and electrons at the point of contact. The laser beam also exhibited sufficient energy to dissociate the bonds of the respective solvents. In the case of acetonitrile, the oxidized Cu-ions bonded with CN− to produce CuCN with a cube-like surface structure. Other nitrile solvents generated spherically-shaped Cu@graphitic carbon (Cu@GC) nanoparticles. Thus, the production of CuCN was favorable only in acetonitrile due to the availability of the cyano group immediately after the fragmentation of acetonitrile (CH3+ and CN−) under PLAL. Conversely, propionitrile and butyronitrile released large amounts of hydrocarbons, which deposited on Cu NPs surface to form GC layers. Following the encapsulation of Cu NPs with carbon shells, further interaction with the cyano group was not possible. Subsequently, theoretical study on the binding energies of nitrile solvents was confirmed by highly correlated basic sets of B3LYP and MP2 which results were consistent with the experimental outcomes. The findings obtained herein could be utilized for the development of novel metal–polymer materials.

A novel hierarchical solution-processed fractional structured molybdenum oxide (MoO3) catalyst is fabricated from tricarbonyltris (propionitrile) molybdenum and used as the counter electrode of all-solid-state fiber-shaped dye-sensitized solar cells (S-FDSSC). The Tafel plot results and electrical impedance spectroscopy suggest that the use of the fractional structured MoO3 catalyst enhances the efficiency of the reduction of I3− to 3I− at the counter electrode/electrolyte interface. Because of the improvements of the short-current circuit and fill factor, the power conversion efficiency of the MoO3-modified S-FDSSC improves by 60% compared with that of the reference S-FDSSC. In addition, because of the robust fractional structure of MoO3, the MoO3-modified S-FDSSC maintains 90% and 95% of efficiency after 350-fold bending and the incident light angle dependency test, respectively. At 65% humidity and at 65 °C, the power conversion efficiency of the MoO3-modified device decreases by

The [3+2] cycloaddition (32CA) reaction of benzonitrile oxide to α-methylene cyclopentanone and propionitrile oxide to γ-methyl-α-methylene-γ-butyrolactone, yielding regio- and stereochemically defined spiroisoxazolines, has been studied at the MPWB1K/6-311G(d,p) computational level. These processes proceed by a one-step mechanism through asynchronous transition states. Ortho regioselectivity and anti diastereofacial selectivity are predicted in complete agreement with the experimental outcomes.

An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived “green” solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour−1.

Understanding the factors that influence ion-solvent properties for the fluoride ion in organic solvents is key to the development of useful liquid electrolytes for fluoride-ion batteries. Using both experimental and computational methods, we examined a range of chemical and electrochemical properties for a set of organic solvents in combination with dry N,N,N-trimethylneopentylammonium fluoride (Np₁F) salt. Results showed that solvent electronic structure strongly influences Np₁F dissolution, and the pK_a of solvent protons provides a good guide to potential F⁻ reactivity. We found a number of organic solvents capable of dissolving Np₁F while providing chemically-stable F⁻ in solution and characterized three of them in detail: propionitrile (PN), 2,6-difluoropyridine (2,6-DFP), and bis(2,2,2-trifluoroethyl) ether (BTFE). Arrhenius analysis for Np₁F/PN, Np₁F/DFP, and Np₁F/BTFE electrolytes suggests that DFP facilitates the highest F⁻ ion mobility of the three neat solvents. Electrolyte mixtures of BTFE and amide co-solvents exhibit higher ionic conductivity than the neat solvents. This improved ionic conductivity is attributed to the ability of BTFE:co-solvent mixtures to partition between Np₁⁺ and F⁻ ion-aggregates, promoting better ion dissociation.

FTIR spectroscopic studies has been carried out on pure toluene (TOL), propionitrile (PN) and their equimolar binary solution at room temperature. DFT calculations (using B3LYP functional with the Grimme's dispersion correction D3 and ωB97XD with the D2 version of Grimme's dispersion) have also been carried out on PN dimers and various TOL-BN heteroassociated networks that are supposed to exist in neat PN and binary solution, respectively, on the basis of the shifts suffered by the fundamental absorptions of TOL and PN upon mixing with each other. Formation of ( m e t h y l ) C − H ⋯ N ≡ C and ( m e t h y l e n e ) C − H ⋯ N ≡ C hydrogen bonded dimers in neat PN has been identified. The dominant interaction forces that stabilize the 1:2 (TOL: PN) complex formed in the binary solution are ( T O L m e t h y l ) C − H ⋯ N ≡ C and ( T O L r i n g ) C − H ⋯ N ≡ C intermolecular H-bonds.

Two complexes of [Cu(L)H2O](ClO4)2, 1 and [Cu(L)H2O](NO3)2, 2 containing hemilabile tetradentate ligand of 3,3'-(piperazine-1,4-diyl)dipropanamide, L, were synthesized and characterized by elemental analyses, spectroscopic (IR, UV–Vis, X-ray) data, molar conductance measurements and X-ray crystallography. The solvatochromic behavior of complex 1 was examined in the selected solvents (nitromethane, acetonitrile, propionitrile, acetone, tetrahydrofuran, ethanol, methanol, dimethylformamide, dimethylsulfoxide, and hexamethylphosphorictriamide), observing positive solvatochromism. The observed solvatochromism was analyzed by a statistical method. The obtained results confirm that the donor number (DN) parameter has the dominant contribution in the observed solvatochromism. For cationic complex 2 density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations was carried out to explore the mechanism of the solvatochromic behavior of the complex and satisfactory theoretical–experimental agreement was achieved. Additional information about the relative stability of Cu N(amide) over Cu O(amide) isomers was obtained by DFT analysis. The complexes were also observed to exhibit thermochromism in the solvent of dimethyl sulfoxide.