Butyronitrile Research Articles

Dielectric and hydrogen bonding studies of butyronitrile with 1,4-dioxane using a time-domain reflectometry

Using time-domain reflectometry (TDR), the complex permittivity of binary mixture of butyronitrile (BTN) and 1,4-dioxane (1,4-DX) at various temperatures and solvent proportions was determined over the frequency range of 10 MHz to 30 GHz. The complex permittivity spectra (CPS) have been fitted to the Havrilik–Negami equation. The relaxation time (τ) and static dielectric constant (ε0) have been calculated for each concentration using the least squares fit method. The nonlinear behavior of dielectric parameters suggests a change in the molecular size and intermolecular bonding of BTN–1,4-DX mixtures. Theoretical static dielectric constants (ε0) have been determined using hydrogen bonded model suggested by Luzar for all solvent proportions and compared with experimental values obtained from TDR.

Conformer Distributions of n-Propyl Cyanide in the Gas Phase and Following Ice Sublimation Measured by Broadband Rotational Spectroscopy

Conformer Distributions of <i>n</i>-Propyl Cyanide in the Gas Phase and Following Ice Sublimation Measured by Broadband Rotational Spectroscopy

The use of a tertiary solvent mixture to study solvent dynamic effects in the photoinduced electron transfer reaction of excited singlet pyrene and indole

The solvent dynamic effects in the PET reactions were studied in a series of tertiary solvent mixtures PA/BN/DEP, spanning a wide range of dielectric constants (5.90 &lt; εs &lt; 23.4) while maintaining refractive index and viscosity constant.

Propyl-cyanide isomer formation on interstellar ices from radical association: a quantum theoretical study

ABSTRACT Both linear and branched isomers of propyl cyanide (PrCN; C3H7CN) are ubiquitous in interstellar space. To date, PrCN is one of the most complex molecules found in the interstellar medium. Furthermore, it is the only one observed species to share the branched atomic backbone of amino acids, some of the building blocks of life. Radical–radical chemical reactions are examined in detail using density functional theory, ab initio methods, and the energy resolved master equation formalism to compute rate constants at a low pressure value prevalent in the ISM. Quantum chemical studies are reported for both isomers considering two possibilities: the gas phase association and the surface reactions of radicals on a 34-water amorphous ice model. The reaction mechanism involves the following radicals association: CH3CHCH3 + CN, CH3 + CH3CHCN and CH3CH2 + CH2CN, CH3 + CH2CH2CN, CN + CH3CH2CH2 for iso-PrCN and n-PrCN formation, respectively. Two DFT methods: M062X and ωB97XD with the 6-311++G(d,p) basis set were tested for reactions in gas phase and on the ice mantle. In the gas phase, MP2/aug-cc-pVTZ level of theory is also used, and the energetics of the five reactions are calculated using explicitly correlated coupled cluster (CCSD(T)-F12) method. All reaction paths are exoergic and barrierless in the gas phase and on the ice-model, suggesting that the formation of iso-PrCN and n-PrCN is efficient on the ice model adopted in this paper. The gas phase rate constants of formation of both isomers can be eventually used as a high limit for the solid state reactions.

Buffer gas cooled ice chemistry. I. Buffer gas cell and mm-wave spectrometer.

A new instrument is described that will employ buffer gas cooling with mm-wave rotational spectroscopy (60-90GHz) to probe molecules desorbed from astrochemical ices prepared in an ultrahigh vacuum environment. Here the design and performance of the buffer gas cell, mm-wave spectrometer and data acquisition system are reported, while application to molecules desorbed from ice surfaces will be described in a future publication. The effective temperature of the neon-cooled buffer gas cell is determined by monitoring a range of rotational lines of propyl cyanide introduced into the cell. Its number density is estimated from comparison to room temperature measurements and the effective collision cross section with neon is estimated by monitoring the free induction decay (FID) lifetimes. The spectrometer and data acquisition system described are capable of acquiring and time-domain averaging the FIDs at 10 Gs/s, 10 bit vertical resolution and 98% duty cycle.

Interstellar detection and chemical modeling of iso-propanol and its normal isomer

Context.The detection of a branched alkyl molecule in the high-mass star forming protocluster Sagittarius (Sgr) B2(N) permitted by the advent of the Atacama Large Millimeter/submillimeter Array (ALMA) revealed a new dimension of interstellar chemistry. Astrochemical simulations subsequently predicted that beyond a certain degree of molecular complexity, branched molecules could even dominate over their straight-chain isomers.Aims.More generally, we aim to probe further the presence in the interstellar medium of complex organic molecules with the capacity to exhibit both a normal and iso form, via the attachment of a functional group to either a primary or secondary carbon atom. Methods. We used the imaging spectral line survey ReMoCA performed with ALMA at high angular resolution and the results of a recent spectroscopic study of propanol to search for the iso and normal isomers of this molecule in the hot molecular core Sgr B2(N2). We analyzed the interferometric spectra under the assumption of local thermodynamical equilibrium. We expanded the network of the astrochemical model MAGICKAL to explore the formation routes of propanol and put the observational results in a broader astrochemical context.Results.We report the first interstellar detection of iso-propanol, ¿-C3H7OH, toward a position of Sgr B2(N2) that shows narrow linewidths. We also report the first secure detection of the normal isomer of propanol, n-C3H7OH, in a hot core. Iso-propanol is found to be nearly as abundant as normal-propanol, with an abundance ratio of 0.6 which is similar to the ratio of 0.4 that we obtained previously for iso- and normal-propyl cyanide in Sgr B2(N2) at lower angular resolution with our previous ALMA survey, EMoCA. The observational results are in good agreement with the outcomes of our astrochemical models, which indicate that the OH-radical addition to propylene in dust-grain ice mantles, driven by water photodissociation, can produce appropriate quantities of normal- and iso-propanol. The normal-to-iso ratio in Sgr B2(N2) may be a direct inheritance of the branching ratio of this reaction process.Conclusions.The detection of normal- and iso-propanol and their ratio indicate that the modest preference for the normal form of propyl cyanide determined previously may be a more general feature among similarly sized interstellar molecules. Detecting other pairs of interstellar organic molecules with a functional group attached either to a primary or secondary carbon may help in pinning down the processes that dominate in setting their normal-to-iso ratios. Butanol and its isomers would be the next obvious candidates in the alcohol family, but their detection in hot cores will be challenging.

Understanding the Role of SEI Layer in Low-Temperature Performance of Lithium-Ion Batteries.

Low-temperature electrolytes (LTEs) have been considered as one of the most challenging aspects for the wide adoption of lithium-ion batteries (LIBs) since the SOA electrolytes cannot sufficiently support the redox reactions at LT resulting in dramatic performance degradation. Although many attempts have been taken by employing various noncarbonate solvent electrolytes, there was a lack of fundamental understanding of the limiting factors for low-temperature operations (e.g., -20 to -40 °C). In this paper, the crucial role of the solid-electrolyte-interface (SEI) in LIB performance at low temperature using a butyronitrile (BN)-based electrolyte was demonstrated. These results suggested that an additive formed SEI with low resistance and low charge transfer dictates the LT performance in terms of capacity and cycle life, presenting a useful guideline in designing new electrolytes to address the LT issue.

Boosting practical high voltage lithium metal batteries by butyronitrile in ether electrolytes via coordination, hydrolysis of C[tbnd]N and relatively mild concentration strategy

Currently ether solvents have been regarded as the most compatible organic solvents with lithium metal in electrolytes of lithium batteries. However, ether solvents are unstable under high voltage (>4.0 V), and prone to side reactions with nickel-rich high-voltage cathode materials. In this work, a novel dual-solvent electrolyte in ethylene glycol dimethyl ether (DME) and butyronitrile (BN) mixed solvent was designed and fabricated for Li/LiNi0.5Mn0.3Co0.2O2-based lithium metal batteries. When charged to high voltage 4.3 V, the battery cycled in this optimal electrolyte can maintain the capacity at 133.7 mAh g−1 with a retention of 88.84% after 150 cycles at 0.2 C and −10 °C. During long-term cycling, the battery also exhibits excellent cycling performance with capacity maintained at about 112.0 mAh g−1 after 500 cycles at 1 C and −10 °C. BN has strong oxidation resistance and high conductivity, which can inhibit the decomposition of ether solvents under high voltage and improve the low temperature performance of battery effectively. Additionally, the cyano (–CN) group in BN molecular has a strong coordination ability with the high-valent metal ions and can mask the active ions on the cathode, correspondingly reducing the corrosion of cathode material by the electrolyte. Moreover, cyano group can participate in the hydrolysis to remove trace amounts of water and acidic by-products such as HF in the electrolyte. Therefore, the boosting effect of butyronitrile for ether solvents can provide a promising strategy for enhancing the performance of high voltage lithium metal batteries for practical industrialization.

Analysis of Chemical Composition and In Vitro and In Vivo Antifungal Activity of Raphanus raphanistrum Extracts against Fusarium and Pythiaceae, Affecting Apple and Peach Seedlings.

The goal of this investigation was to evaluate the in vitro and in vivo efficiency of Raphanus raphanistrum extracts against Fusarium and Pythiaceae species associated with apple and peach seedling decline in Tunisian nurseries. A chemical composition of organic extracts was accomplished using liquid chromatography, thin layer chromatography, and gas chromatography analysis. The in vitro test of three aqueous extract doses of R. raphanistrum against some apple and peach decline agents showed its efficacy in reducing mycelia growth. The in vivo assay of fine powder of this plant on peach seedlings revealed that treatment 8-weeks before the inoculation and planting was more efficient than the treatment before one week. This experiment revealed that the root weight of peach seedlings inoculated by F. oxysporum was improved to 207.29%. For apple seedlings, the treatment 8 weeks before the inoculation and plantation was more efficient than the treatment one week before; it reduced the root browning index. The study of R. raphanistrum chemical composition and its efficiency showed that the glucosinolates products: nitrile (4-Hydroxy-3-(4-methylphenylthio) butane nitrile, benzene acetonitrile, 4-fluoro,butane nitrile, 4-hydroxy-3-[(4-methylphenyl) thio] nitrile), and thiocyanate molecules (thiocyanic acid, ethyle) are responsible for the anti-fungal activities.

Quantum chemical study on the formation of isopropyl cyanide and its linear isomer in the interstellar medium

AbstractThe formation mechanism of linear and isopropyl cyanide (hereafter n-PrCN and i-PrCN, respectively) in the interstellar medium (ISM) has been proposed from the reaction between some previously detected small cyanides/cyanide radicals and hydrocarbons/hydrocarbon radicals. n-PrCN and i-PrCN are nitriles therefore, they can be precursors of amino acids via Strecker synthesis. The chemistry of i-PrCN is especially important since it is the first and only branched molecule in ISM, hence, it could be a precursor of branched amino acids such as leucine, isoleucine, etc. Therefore, both n-PrCN and i-PrCN have significant astrobiological importance. To study the formation of n-PrCN and i-PrCN in ISM, quantum chemical calculations have been performed using density functional theory at the MP2/6-311++G(2d,p)//M062X/6-311+G(2d,p) level. All the proposed reactions have been studied in the gas phase and the interstellar water ice. It is found that reactions of small cyanide with hydrocarbon radicals result in the formation of either large cyanide radicals or ethyl and vinyl cyanide, both of which are very important prebiotic interstellar species. They subsequently react with the radicals CH2 and CH3 to yield n-PrCN and i-PrCN. The proposed reactions are efficient in the hot cores of SgrB2 (N) (where both n-PrCN and i-PrCN were detected) due to either being barrierless or due to the presence of a permeable entrance barrier. However, the formation of n-PrCN and i-PrCN from the ethyl and vinyl cyanide always has an entrance barrier impermeable in the dark cloud; therefore, our proposed pathways are inefficient in the deep regions of molecular clouds. It is also observed that ethyl and vinyl cyanide serve as direct precursors to n-PrCN and i-PrCN and their abundance in ISM is directly related to the abundance of both isomers of propyl cyanide in ISM. In all the cases, reactions in the ice have smaller barriers compared to their gas-phase counterparts.

Selective one-pot synthesis of asymmetric secondary amines via N-alkylation of nitriles with alcohols

The synthesis of asymmetric secondary amines (ASA) is commonly achieved by N-alkylation of primary amines with alcohols. Here, we investigated the ASA synthesis via the direct amination of alcohols with nitriles, which avoids the synthesis, separation and purification of the primary amines in a first step. Specifically, the ASA synthesis via N-alkylation of butyronitrile (BN) with primary (n-propanol, iso-butanol and n-octanol) and secondary (2‐propanol, 2‐butanol and 2‐octanol) alcohols was studied on SiO2-supported Co, Ni and Ru catalysts. Competitive BN hydrogenation‐condensation reactions formed dibutylamine (the symmetric secondary amine) and tertiary amines as main secondary products. On Co/SiO2, the ASA selectivities for BN/primary alcohol reactions were between 49 and 58% at complete BN conversion, forming dibutylamine and tertiary amines as byproducts. For BN/secondary alcohol reactions, Co/SiO2 formed selectively (ASA + dibutylamine) mixtures containing 78–85% of ASA, thereby showing that the alcohol amination with nitriles is an attractive alternative route for the synthesis of valuable asymmetric secondary amines.

Rotational rest frequencies of the low lying vibrational states of n-propyl cyanide from extensive laboratory measurements up to 506 GHz

Context. The spectra of four low-lying vibrational states of both anti and gauche conformers of normal-propyl cyanide were previously measured and analyzed in two spectral windows between 36 and 127 GHz. All states were then identified in a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. Aims. We wanted to extend the measurements and analysis up to 506 GHz to provide accurate predictions over a much wider range of frequencies, quantum numbers and energies. Methods. We carried out measurements in two additional frequency windows up to 506 GHz. Results. For the gauche conformer, a large number of both a- and b-type transitions were identified. For the anti conformer, transitions were predominantly, but not exclusively, a-type. We hence improved molecular parameters for the ground states of both anti- and gauche-n-propyl cyanide and for excited vibrational states of the gauche conformer (v30 = 1, v29 = 1, v30 = 2, v28 = 1) and anti conformer (v30 = 1, v18 = 1, v30 = 2, v29 = 1) with high order coupling parameters determined between v18 = 1 and v30 = 2. Parameters are published for the first time for v18 = v30 = 1 of the anti conformer and for v29 = v30 = 1 of the gauche conformer. Conclusions. In total 15385 lines have been incorporated in the fits and should allow good predictions for unperturbed lines over the whole operating range of radio-telescopes. Evidence is found for vibrational coupling for some levels above 380 GHz. The coupling between v18 = 1 and v30 = 2 of the anti conformer has been well characterized. An additional list of 740 lines showing potential but as yet unidentified coupling has been provided for astrophysical identification.

Understanding propyl cyanide and its isomers formation: ab initio study of the spectroscopy and reaction mechanisms.

Recent detection of propyl cyanide (C3H7CN) with both linear and branched structures has stimulated many experimental and theoretical studies. In this theoretical work, we present the spectroscopic properties of the far infrared spectra of these species and we investigate their different paths of formation in the gas phase. Our spectroscopic study concerns the far infrared spectra of iso, anti and gauche propyl cyanide isomers. The equilibrium structures and the potential energy surfaces are calculated using explicitly correlated cluster ab initio methods (CCSD(T)-F12) and a variational procedure designed for non-rigid species and large amplitude motions. Accurate rotational constants, centrifugal distortion constants, potential energy barriers and surfaces are provided. The rovibrational parameters in the ground vibrational states compare very well with experimental data. The low energy vibrational levels correspond to torsional modes. Far infrared energies are calculated up to 500 cm-1 using the variational approach and the vibrational second order theory (VPT2), and a good agreement with previous experimental values is found. We have also investigated the gas phase formation of the different C3H7CN isomers. After several trials of reacting gaseous species, we considered that a possible formation route of the C3H7CN isomers can be from the bimolecular reaction of HCN with propene. At the UMP2(full)/aug-cc-pVTZ level of theory, this reaction involves two steps for each isomer; the first one corresponds to the association of the two radicals while the second one corresponds to H transfer. From highly correlated ab initio calculations by means of CCSD(T)/aug-cc-pVTZ//UMP2(full)/aug-cc-pVTZ, the geometries, energetics and minimum energy paths of the reactions are obtained. Also, the first step's transition state disappears, as the diradical minimum is much less stabilized with UCCSD(T) than by UMP2(full). We employ the zero curvature tunneling and canonical variational (CVT/ZCT) semiclassical method to predict rate constants for propyl cyanide isomers formation in the gas phase. However, due to the presence of a significant barrier, this reaction leads to very small rate constants. Very recently, we probed reaction mechanisms involving radical addition and we found that these reactions are barrierless and highly exothermic leading to expected fast reactive processes for the formation of propyl cyanide products. The kinetics of such diradical reactions is under study.

Rotational spectrum of 3-aminopropionitrile and searches for it in Sagittarius B2(N)

Aminoacetonitrile (NH2CH2CN) was detected in the interstellar medium (ISM) one decade ago in the course of a spectral survey of the hot molecular core Sagittarius (Sgr) B2(N) with the IRAM 30 m telescope. With the advent of sensitive telescopes such as the Atacama Large Millimeter/submillimeter Array (ALMA), the degree of chemical complexity in the ISM can be further explored. In the family of aminoacetonitrile, the next stage in complexity with one additional CH2 group is aminopropionitrile. This molecule has two structural isomers, a chain-like (3-aminopropionitrile, NH2CH2CH2CN) and a branched, chiral one (2-aminopropionitrile, CH3CH(NH2) CN). The latter was studied in the laboratory a few years ago and was not detected in the IRAM 30 m survey. We present the search for both isomers in the EMoCA (Exploring Molecular Complexity with ALMA) survey, a sensitive spectral survey of Sgr B2(N) performed with ALMA. The rotational spectrum of 3-aminopropionitrile has been recorded in laboratory with a submillimeter spectrometer using solid-state sources. Helped by ab initio calculations performed for the different possible conformations, we present here the analysis based on a Watson Hamiltonian for an asymmetric one-top rotor in A-reduction performed in the frequency range 150–500 GHz for two conformers. More than 6200 lines of the ground-state and lowest excited vibrational states, corresponding to more than 8200 transitions, were assigned in the experimental spectrum. Partition functions, including the vibrational contribution of these states, and predictions in the JPL-CDMS catalog format were determined in order to search for both conformers of 3-aminopropionitrile in Sgr B2(N). Neither 3-aminopropionitrile, nor 2-aminopropionitrile are detected. The derived upper limits imply that they are at least 12 and 5 times less abundant than aminoacetonitrile, respectively. A comparison to ethyl cyanide and n-propyl cyanide detected in this source suggests that an improvement by a factor three in sensitivity may be sufficient to detect 3-aminopropionitrile, which should be within the range of our on-going follow-up project with ALMA.

Rotational Spectroscopy of the Lowest Energy Conformer of 2-Cyanobutane.

Isopropyl cyanide was recently detected in space as the first branched alkyl compound. Its abundance with respect to n-propyl cyanide in the Galactic center source Sagittarius B2(N2) is about 0.4. Astrochemical model calculations suggest that for the heavier homologue butyl cyanide the branched isomers dominate over the unbranched n-butyl cyanide and that 2-cyanobutane is the most abundant isomer. We have studied the rotational spectrum of 2-cyanobutane between 2 and 24 GHz using Fourier transform microwave spectroscopy and between 36 and 402 GHz employing (sub)millimeter absorption spectroscopy. Transitions of the lowest energy conformer were identified easily. Its rotational spectrum is very rich, and the quantum numbers J and Ka reach values of 111 and 73, respectively. This wealth of data yielded rotational and centrifugal distortion parameters up to tenth order, diagonal and one off-diagonal 14N nuclear quadrupole coupling parameters, and one nuclear spin-rotation coupling parameter. We have also carried out quantum chemical calculations in part to facilitate the assignments. The molecule 2-cyanobutane was not found in the present ALMA data of Sagittarius B2(N2), but it may be found in the more sensitive data that have been completed very recently in the ALMA Cycle 4.

Exploring molecular complexity with ALMA (EMoCA): Simulations of branched carbon-chain chemistry in Sgr B2(N)

Using mm-wavelength data from ALMA, the EMoCA spectral line survey revealed the presence of both the straight-chain and branched forms of propyl cyanide (C$_3$H$_7$CN) toward the Galactic Center star-forming source Sgr B2(N2). This was the first interstellar detection of a branched aliphatic molecule. Through computational methods, we seek to explain the observed $i$:$n$ ratio for propyl cyanide, and to predict the abundances of the four different forms of the homologous nitrile, butyl cyanide (C$_4$H$_9$CN). We also investigate whether other molecules will show a similar degree of branching, by modeling alkanes up to pentane (C$_5$H$_{12}$). We use a coupled three-phase chemical kinetics model to simulate the chemistry of Sgr B2(N2), using an updated chemical network that includes grain-surface/ice-mantle formation routes for branched nitriles and alkanes. We use the EMoCA survey data to search for the straight-chain form of butyl cyanide toward Sgr B2(N2). The observed $i$:$n$ ratio for propyl cyanide is reproduced by the models. Butyl cyanide is predicted to show similar abundances to propyl cyanide, and to exhibit strong branching, with the $sec$ form clearly dominant over all others. The addition of CN to acetylene and ethene is found to be important to the production of vinyl, ethyl, propyl, and butyl cyanide. We report a non-detection of $n$-C$_4$H$_9$CN toward Sgr B2(N2), with an abundance at least 1.7 times lower than that of $n$-C$_3$H$_7$CN. This value is within the range predicted by the chemical models. The models indicate that the degree of branching rises with increasing molecular size. The efficiency of CN addition to unsaturated hydrocarbons boosts the abundances of nitriles in the model, and enhances the ratio of straight-to-branched molecule production. The predicted abundance of $s$-C$_4$H$_9$CN makes it a good candidate for future detection toward Sgr B2(N2).

Simulations of branched carbon-chain chemistry in star-forming regions

AbstractThe detection of iso-propyl cyanide (i-C3H7CN) toward the Galactic Center hot-core source Sgr B2(N) (by Belloche et al. 2014) marked the first interstellar detection of an aliphatic molecule with a branched carbon-chain structure. Surprisingly, this branched form was found to have an almost equal abundance with its straight-chain homologue, normal-propyl cyanide (i:n = 0.40 ± 0.06). The detection of this first example of an interstellar molecule with a side-chain raises the question as to how prominent such structures may be in interstellar chemistry, and whether the large branched-to-straight chain ratio is maintained for even larger molecules.Here are presented recently published models that simulate the chemistry occurring in Sgr B2(N) using a chemical network that explicitly includes the straight-chain and branched forms of propyl cyanide (normal/iso) and butyl cyanide (normal/iso/sec/tert), as well as butane (n/i) and pentane (n/i/neo). Formation is assumed to occur on dust-grain surfaces, but a full complement of destruction mechanisms is included both on the grains and in the gas phase.The models suggest that branched structures become increasingly dominant as molecular sizes increase. In the case of butyl cyanide, the sec form is at least ∼2 times more abundant than the straight-chain normal form, and together the branched forms dominate normal-butyl cyanide by a factor of at least 3. The results for the larger alkanes suggest similarly large ratios of branched to straight-chain molecules. A key set of reactions in the surface/ice chemistry of interstellar nitriles is found to be the addition of the CN radical to unsaturated hydrocarbons, especially acetylene and ethene. The models also predict that the dominant, sec form of butyl cyanide reaches a peak abundance equal to that of n-propyl cyanide, albeit with a smaller emission radius. This makes s-C4H9CN a good candidate for detection. New ALMA observations to search for this molecule are ongoing.

Laboratory spectroscopic study and astronomical detection of vibrationally excitedn-propyl cyanide

We performed a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius~B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. We determined line intensities of n-propyl cyanide in the ground vibrational states of its gauche and anti conformers toward the hot molecular core Sagittarius B2(N2) which suggest that we should also be able to detect transitions pertaining to excited vibrational states. We wanted to determine spectroscopic parameters of low-lying vibrational states of both conformers of n-propyl cyanide to search for them in our ALMA data. We recorded laboratory rotational spectra of n-propyl cyanide in two spectral windows between 36 and 127 GHz. We searched for emission lines produced by these states in the ALMA spectrum of Sagittarius B2(N2). We modeled their emission and the emission of the ground vibrational states assuming local thermodynamic equilibrium (LTE). We have made extensive assignments of a- and b-type transitions of the four lowest vibrational states of the gauche conformer which reach J and Ka quantum numbers of 65 and 20, respectively. We assigned mostly a-type transitions for the anti conformer with J and Ka quantum numbers up to 48 and 24, respectively. Rotational and Fermi perturbations between two anti states allowed us to determine their energy difference. The resulting spectroscopic parameters enabled us to identify transitions of all four vibrational states of each conformer in our ALMA data. The emission features of all states, including the ground vibrational state, are well-reproduced with the same LTE modeling parameters, which gives us confidence in the reliability of the identifications, even for the states with only one clearly detected line.

Magnetic field effect on exciplex-forming organic acceptor/donor system: a powerful tool for understanding the preferential solvation

Many acceptor/donor systems can form excited-state charge-transfer complexes (exciplexes) in photo-induced electron transfer reactions. Exciplex can be detected by their luminescence. In addition, the exciplex luminescence is magneto-sensitive. Here, we employ an approach based on the magnetic field effect on the exciplex of 9,10- dimethylanthracene/N,N-dimethylaniline pair in micro-homogeneous and micro-heterogeneous binary solvents to investigate the effects of the preferential solvation processes on solute molecules in solutions. Micro-homogeneous solvent mixtures of propyl acetate (PA)/butyronitrile (BN) allow for a systematic variation of the static dielectric constants, s , in the range from 6.0 to 24.6. The mixtures of toluene (TO)/dimethylsulfoxide (DMSO) with varying the s values in the range from 4.3 to 15.5 are used as micro-heterogeneous binary solvents. In micro-heterogeneous environment, DMSO molecules get preferentially favoured in the solvation shell, forming micro-clusters surrounding the solute molecules. This solvation effect is reflected in the altered magnetic field effects, lifetimes and dissociation rate constants of the exciplexes.

(Invited) Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface. In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time. In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1). Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.