Cationic Species Research Articles

Hydroxylated Polyoxometalate with Cu(II)- and Cu(I)-Aqua Complexes: A Bifunctional Catalyst for Electrocatalytic Water Splitting at Neutral pH.

A sole inorganic framework material [Li(H2O)4][{CuI(H2O)1.5} {CuII(H2O)3}2{WVI12O36(OH)6}]·N2·H2S·3H2O (1) consisting of a hydroxylated polyoxometalate (POM) anion, {WVI12O36(OH)6}6-, a mixed-valent Cu(II)- and Cu(I)-aqua cationic complex species, [{CuI(H2O)1.5}{CuII(H2O)3}2]5+, a Li(I)-aqua complex cation, and three solvent molecules, has been synthesized and structurally characterized. During its synthesis, the POM cluster anion gets functionalized with six hydroxyl groups, i.e., six WVI-OH groups per cluster unit. Moreover, structural and spectral analyses have shown the presence of H2S and N2 molecules in the concerned crystal lattice, formed from "sulfate-reducing ammonium oxidation (SRAO)". Compound 1 functions as a bifunctional electrocatalyst exhibiting oxygen evolution reaction (OER) by water oxidation and hydrogen evolution reaction (HER) by water reduction at the neutral pH. We could identify that the hydroxylated POM anion and copper-aqua complex cations are the functional sites for HER and OER, respectively. The overpotential, required to achieve a current density of 1 mA/cm2 in the case of HER (water reduction), is found to be 443 mV with a Faradaic efficiency of 84% and a turnover frequency of 4.66 s-1. In the case of OER (water oxidation), the overpotential needed to achieve a current density of 1 mA/cm2 is obtained to be 418 mV with a Faradaic efficiency of 80% and turnover frequency of 2.81 s-1. Diverse electrochemical controlled experiments have been performed to conclude that the title POM-based material functions as a true bifunctional catalyst for electrocatalytic HER as well as OER at the neutral pH without catalyst reconstruction.

Looking into the ion-selective nanoptode bulk – Alternative mechanism of optical signal transduction for ratiometric ion-selective probes applicable in broad pH range

Ion-selective sensors, including optodes, explore ion-exchange at the interface to observe analyte ion binding to neutral ionophore in the probe bulk. Typically the optical transducer used is a charged dye - incorporation of analyte cation requires expulsion of positively charged ion from the probe, the process is giving rise to observable optical signal. We propose an alternative approach focused on the probe bulk and allowing application of uncharged dye as the optical transducer. The neutral solvatochromic dye is not involved in maintaining electroneutrality, but its optical spectrum reflects local changes occurring in the probe bulk in response to analyte incorporation, giving rise to analytical signal dependent on the analyte concentration changes in the sample. The proposed optical transduction mechanism offers increase of emission for increase of analyte contents in the sample in a broad concentration range, a linear dependence of optical signal on logarithm of concentration was observed. Moreover, this approach results in significant benefits: it mitigates the cross sensitivity to hydrogen ions concentration changes observed for classical optodes, allowing application of probes in unbuffered samples as well as in wide pH range, including acidic solution. The system requires the presence of adjunctive, cationic species in the probe, that are exchanged for analyte cations preferred in the system due to interactions with ionophore. Depending on the choice of adjunctive cation ratiometric sensing can be achieved. It is also shown that such system does not require the presence of a surfactant, yet allows formation of stable emulsion of nanoprobes.

3-Alkoxyphthalides as Nonhomopolymerizable, Highly Reactive Comonomers for ABC Pseudo-Periodic Terpolymers and Degradable Polymers via Cationic Co- and Terpolymerizations with Oxiranes and/or Vinyl Ethers

3-Alkoxyphthalides (ROPTs) are promising candidate monomers that react with a cationic species at the carbonyl group and subsequently undergo ring-opening to generate a carbocation adjacent to both aryl and alkoxy groups (oxocarbenium ion). In this study, cationic polymerizations of ROPTs bearing methoxy, isopropoxy, tert-butoxy, or phenoxy groups were investigated with a particular focus on the copolymerizations with oxiranes. Cationic homopolymerization of ROPTs did not occur under any of the examined conditions. In contrast, cationic copolymerizations of ROPT with oxiranes, such as 4-vinyl-1-cyclohexene-1,2-epoxide (VCHO), proceeded smoothly via very frequent crossover reactions. The copolymers could be degraded under acidic conditions due to the cleavage of the acetal moieties generated by the crossover reactions from ROPT to VCHO. Cationic copolymerizations of ROPT with most of the examined vinyl ethers (VEs) and styrene derivatives did not proceed, likely due to inefficient crossover reactions from the vinyl monomers to ROPT. However, cationic terpolymerizations of VE, oxirane, and ROPT successfully proceeded via highly selective crossover reactions, resulting in ABC-type pseudo-periodic terpolymers under optimized conditions.

Chromophores assisted phytochemicals and pheromones coatings on porous inorganic layers for enhancing anti-corrosion and photocatalytic properties

This work aims to enhance the anti-corrosion and photocatalytic activity of porous inorganic layers through a novel approach involving the exploitation of chromophores derived from phytochemicals and pheromones. Herein, organic acid (carminic acid) and organic salt (indigo carmine) obtained from pheromones and phytochemicals, respectively, are utilized to modulate the porous surface of inorganic layers produced on AZ31 Mg alloy via plasma electrolytic oxidation. Such pheromones and phytochemicals coatings have a double link inside them along with negatively charged functional groups, which enabled the sealing of the sponge-like structure of the inorganic layer through a couple of bonding mechanisms, such as hydrogen bonding, π-π interaction, as well as electrostatic interactions between polar parts of such organic molecules and cationic species generated from the inorganic layer. The phytochemical coating exhibited superior electrochemical stability compared to other samples, as demonstrated by its high polarization resistance (1.27 × 10+8 Ω.cm+2). Additionally, the phytochemical coating demonstrated the ability to photodegrade methylene blue, achieving a photocatalytic efficiency of 99.47 %. The stacked and parallel interactions of the phytochemical and/or phermonic layer on the surface of inorganic layers were explored with the aid of density functional theory.

Adamantane Annulation to Arenes: A Strategy for Property Modulation of Aromatic π-Systems.

Peripheral structural modifications of arenes are widely used to control or improve the optoelectronic properties, molecular assembly, and stability of aromatic π-materials as well as to explore new functions. However, known modifications are often tedious and complex; therefore, a simple yet powerful modification strategy is needed. We discovered that annulation with a simple adamantane scaffold exerts a significant impact on the properties, alignment, and stability of aromatic π-systems. This unprecedented adamantane annulation was achieved by a two-step transformation of metallated arenes and 4-protoadamantanone, generating a range of adamantane-annulated arenes. Analysis of structural and electronic properties uncovered unique effects of the process, such as high solubility and enhanced conjugation. The oxidation of adamantane-annulated perylenes produced strikingly stable cationic species with emission extended to the near-infrared region. This simple property modulation of aromatic π-systems would not only create potentially ground-breaking π-materials but also novel nanocarbon materials, such as diamond-graphene hybrids.

Development of the P-Arylation of Dithieno[3,2-b : 2',3'-d]phosphole with Aryl Iodonium Salts.

P-Arylation of dithieno[3,2-b : 2',3'-d]phosphole toward cationic phenyl phospholium species using diaryliodonium reagents was explored. Multiple conditions were tested to optimize the reaction, including variation of solvent, temperature, stoichiometry, time, and aryliodonium species employed. Initial use of diphenyliodonium chloride led to an unexpected dithienophosphole Cu(I) chloride complex that was characterized crystallographically. Alternatively, the use of diphenyliodonium hexafluorophosphate in ethanol under microwave conditions led to the successful isolation of the P-arylated target. The phenyl dithienophospholium species exhibits blue luminescence with a quantum yield of 100 % in solution that is considerably red-shifted in the solid state. The photophysics and solid-state organization of the new species were compared with those of a related methyl congener, showing distinct differences that are assigned to the nature of the carbon-based substituent at the phosphorus center, which was also confirmed by DFT calculations, and the supramolecular organization in the solid state.

Direct and indirect contact of an austenitic high-temperature alloy to eutectic chloride melts with possible consequences for inhibitor strategies

There is an inevitable difference between direct and indirect contact of metals with eutectic chloride melts defined by the gas phase impurity content, here, humidity and oxygen in argon. The impurities-to-salt ratio will always be higher in the gas phase allowing for a more aggressive attack on metal components. This effect has been studied on a decommissioned metal container from an experimental high-temperature setup, which has never been in direct contact with a chloride melt but with its evaporated species; the vessel lasted only a short time, 700 h. It was found that the vessel suffered more severe damage when exposed to evaporated salt species than in direct contact with the salt melt; the estimated metal thickness loss per year is higher by almost three-fold than the direct contact. In contrast to 253MA fully immersed in MgCl2-KCl, magnesium has not been the most-active cationic species causing corrosion in the vessel wall exposed to evaporated salt species; instead, it has been potassium. Consequently, this unexpected observation needs to be carefully considered in the design of a Gen3-CSP storage tank and the applied inhibitor strategy.

A method for calculating catalytic-site amount and judging antagonistic/synergetic effect in multi-metallic catalyst

Bimetallic doping is widely utilized to increase the catalytic activity of TiO2-supported catalyst in selective catalytic reduction of nitrogen oxide (SCR). However, a “bimetallic enhancement” is hard to judge since the ratio of active sites, which actually devotes to the catalytic Turnover frequency (TOF, s−1), is difficult to obtain. In this work, Mn, Fe, V, and their pairs were loaded on TiO2, and applied in SCR. Diffuse Reflection Fourier Transform Infrared Spectrometer established a method to evaluate the ratio of working catalytic sites. TOF of these sites were calculated. As a result, single-metallic Mn and V resulted in an average TOF of 0.17 s−1 and 0.11 s−1, respectively, bigger than that (0.10 s−1) of bimetallic MnV. With the increase of loading amount, single-atom cation was agglomerated to form cation pair, and then cluster. Among these three species, cation pair had the biggest TOF, indicating a synergetic effect. Mn obtained the best TOF of 0.18 s−1 at a loading of 1 mmol. One cation species accelerated agglomeration and crystal transformation of the other cation, thus decreasing the TOF and exhibiting an antagonistic effect. These results are in favor of mechanism understanding and catalyst optimization.

Role of pH and cations on emulsion formation and stability of crude oils

Emulsification plays a crucial role in various areas. However, undesirable emulsions, especially water-in-oil (W/O) emulsions, formed during crude oil production, transportation, processing, and stockpiling, become significant issues in the petroleum industry. Various studies have focused on evaluating the factors affecting emulsion stability and their mechanisms, which hardly explain the relationship with emulsion formation. This study assessed the effects of pH and cations on the transformation of emulsion types and their stability based on the observed emulsion formation process and emulsion particle sizes. It was found that the final W/O emulsions were transformed from water-in-oil-in-water (W/O/W) emulsions for all brine conditions. At neutral pH, more W/O emulsions were formed through the transformation of W/O/W emulsion, but the high pH broke down most of the W/O/W emulsion into free water and oil. Emulsion particles’ zeta potential or electrokinetics plays a significant role in W/O/W emulsion stability at high pH. The transformation of emulsion types in cation solutions was similar to neutral pH; the amount of W/O emulsion depends on cation species. The W/O/W emulsion stability under different pH in the following order: neutral pH < low pH < high pH, whereas final W/O emulsion stability is as follows: high pH < low pH < neutral pH; MgCl2 < CaCl2 < NaCl. The stability of the emulsion is influenced by the properties of the crude oil, such as viscosity and TAN/TBN ratio, which affect the oil film thickness of the W/O/W. Based on these findings, a stability mechanism is proposed for the emulsion under different pH and cations.

Multifunctionalized Covalent Organic Frameworks for Broad-Spectrum Extraction and Ultrasensitive Analysis of Per- and Polyfluoroalkyl Substances

The contamination of surface and ground water by per- and polyfluoroalkyl substances (PFASs) has become a growing concern, and the structural diversity of PFASs is the major challenge for their ubiquitous applications. Strategies for monitoring coexistent anionic, cationic, and zwitterionic PFASs even at trace levels in aquatic environments are urgently demanded for effective pollution control. Herein, novel amide group and perfluoroalkyl chain-functionalized covalent organic frameworks (COFs) named COF-NH-CO-F9 are successfully synthesized and used for highly efficient extraction of broad-spectrum PFASs, attributing to their unique structure and the multifunctional groups. Under the optimal conditions, a simple and high-sensitivity method is established to quantify 14 PFASs including anionic, cationic, and zwitterionic species by coupling solid-phase microextraction (SPME) with ultrahigh-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS) for the first time. The established method displays high enrichment factors (EFs) of 66-160, ultrahigh sensitivity with low limits of detection (LODs) of 0.0035-0.18 ng L-1, a wide linearity of 0.1-2000 ng L-1 with correlation coefficient (R2) ≥0.9925, and satisfactory precision with relative standard deviations (RSDs) ≤11.2%. The excellent performance is validated in real water samples with recoveries of 77.1-108% and RSDs ≤11.4%. This work highlights the potential of rational design of COFs with the desired structure and functionality for the broad-spectrum enrichment and ultrasensitive determination of PFASs in real applications.

Cationic Bismuth Amides Add across Activated C═X Bonds (X = C, N, and S): Pronounced Solvent Effects on Reactivity and Selectivity

The reactivity of a literature-known, ring-strained cationic bismuth amide toward the unsaturated substrates RN═C═NR, CS2, and acrylonitrile is reported (R = iPr, Cy, and pTol). Subtle changes in the polarity of the reaction medium (THF vs pyridine) can be exploited to selectively address two different reaction pathways. Either the dinuclear nature of the starting material is preserved, only one substrate molecule per two bismuth atoms is incorporated into the product, and an aryl migration is possible or well-defined mononuclear compounds with a Bi/substrate ration of 1:1 are observed. These findings correlate with an unexpected increase in reactivity of the cationic bismuth species, when the polarity of the solvent is increased from THF to pyridine, and are likely to be connected to the nuclearity of the cationic bismuth amide starting material.

Production of soybean husks activated carbon for basic dye adsorption: characterization, kinetics, equilibrium, and thermodynamic studies

ABSTRACT Soybean husks were used as a precursor to prepare activated carbon (SHAC) by chemical activation with ZnCl2 under different experimental conditions. The best operational conditions for SHAC production were determined using a 23 factorial design and variance analysis (ANOVA). The best results were achieved with an impregnation ratio of 1 g ZnCl2/g soybean husks, a residence time of (180 min), and a temperature of (650ºC), resulting in SHAC with a high surface area (1150 m2/g) and pore volume (0.5933 cm3/g). The selected SHAC was used to adsorb malachite green (MG) from aqueous solutions. The MG adsorption process followed pseudo-second-order kinetics and Langmuir isotherms, with maximum adsorption capacities of 152.53 mg/g, 153.29 mg/g, and 166.83 mg/g at 30°C, 40°C, and 50°C, respectively. Furthermore, the pH of the point of zero charge of the selected SHAC was close to neutral, making it suitable for adsorbing cationic species in basic pH solutions.

One-pot synthesis of stable cationic gold species highly active in the CO oxidation confined into mordenite-like zeolite

The presence of cationic gold species is a key factor for the CO oxidation over the supported gold catalysts based on non-reducible metal oxides. The deactivation of such catalysts is mainly associated with the Au nanoparticles (AuNPs) sintering and the concomitant reduction of cationic Au species. Here we report the high catalytic stability at the CO oxidation of the cationic Au species confined into a mordenite-like zeolite matrix prepared by a one-pot synthesis method. The sample with lowest Au loading (0.32 % wt.) exhibited the higher catalytic performance and stability during CO oxidation. Detailed FTIR analysis showed that the CO oxidation on sample with low Au content (0.32 wt%) occurred preferentially via CO interaction with the cationic interface Au-hydroxyl (Au1+–OH−) species to produce CO2(g) via decarboxylation. In contrast, the sample with a high Au content (1.56 wt%) displayed lower CO oxidation ability, which was associated with a low content and less stability of cationic gold species. Proposed synthesis method permits to obtain in a one-pot way stable cationic gold species highly effectively for the CO oxidation.

Removal of pharmaceutical pollutants from effluent by a plant-based metal–organic framework

Emerging organic contaminants (EOCs), such as pharmaceutical compounds, are of growing environmental concern, and there is a need to develop new materials and technologies for their efficient removal. Here we developed a highly porous and stable zirconium–ellagate framework, denoted SU-102, which was used to remove EOCs from water, including real municipal wastewater treatment plant effluent. SU-102 adsorbs cationic EOCs with particularly high efficiencies, and of the 17 pharmaceutical EOCs detected in wastewater treatment plant effluent, all 9 cationic species were removed with efficiencies of at least 79.0–99.6%, emphasizing the importance of framework charge on selectivity. As a second mechanism of EOC removal, SU-102 photodegraded the antibiotic sulphamethazine under visible light. SU-102 is synthesized from ellagic acid, an edible polyphenol building unit, highlighting the possibility of creating stable high-performance multi-functional materials from sustainably sourced plant-based components.

High Selectivity and Sensitivity in Chemiresistive Sensing of Co(II) Ions with Liquid-Phase Exfoliated Functionalized MoS2 : A Supramolecular Approach.

Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selective sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2':6',2″-terpyridine-4'-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations complexation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm - 1 µm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+ ])-1 combined with a high selectivity towards Co2+ over K+ , Ca2+ , Mn2+ , Cu2+ , Cr3+ , and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors.

The stability and reactivity of neutral and charged aluminium doped carbon clusters (Al1,2C2-70,±)

The stability and reactivity of Al-doped linear and quasi-linear carbon chains (Al1,2C2-70,±) were computationally investigated using various reaction and binding energy parameters. The dissociation of the clusters was studied via the elimination of Al, C from the neutral species, Al0,+, C0,+ the cationic species, and Al0,-, C0,- from the anionic species. The stability was further examined based on electron elimination reactions, such as electron detachment from Al1,2C2-7- and ionization of Al1,2C2-7. The study proceeded by formulating a novel relative energy parameter, which was generated from the binding energy values. The lowest energy dissociation channels of Al1,2C1-70,± were the Al and Al+ elimination from the neutral/anionic and cationic clusters, respectively. Under the dissociation conditions, the even-carbon species (m = 2,4,6) AlCm (doublet), AlCm+ (triplet), AlCm- (singlet), Al2Cm (singlet), Al2Cm+ (doublet) were found to be more stable than that of the odd-carbon clusters (m = 3,5,7), irrespective of the spin states. In the case of Al2Cm-, the odd carbon clusters were found to be more stable. The stability orders based on the widely used highly endothermic C-elimination reaction were found to be significantly different. We have systematically addressed the above disparities and have commented on how to accurately predict the abundance of the species under extreme experimental conditions. The reactivity of Al1,2-doped clusters was found to be higher than the bare carbon chains. Based on the bond-strength parameters calculated using AIM analysis, the Al1,2-doping led to an activated Al-C bond rather than the carbon chains, eventually resulting in reactive meal-carbon clusters. The Al-C bonding was discussed using electron density at the Al-C bond critical points (ρAl-C), the vibrational frequency of the Al-C bond (νAl-C), bond length (rAl-C), the NBO charge on the Al atoms (qAl) and with the molecular orbital diagrams. The results of the current investigations can be highly relevant to astrochemistry, spectroscopy, material, and organometallic chemistry communities.

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations

Highly emissive π-conjugated macrocycles with tunable circularly polarized luminescence (CPL) have sparked theoretical and synthetic interests in recent years. Herein, we report a synthetic approach to obtain new chiral organoborane macrocycles (CMC1, CMC2, and CMC3) that are built on the structurally chiral [5]helicenes and highly luminescent triarylborane/amine moieties embedded into the cyclic systems. These rarely accessible B/N-doped main-group chiral macrocycles show a unique topology dependence of the optoelectronic and chiroptical properties. CMC1 and CMC2 show a higher luminescence dissymmetry factor (glum) together with an enhanced CPL brightness (BCPL) as compared with CMC3. Electronic effects were also tuned and resulted in bathochromic shifts of their emission and CPL responses from blue for CMC1 to the near-infrared (NIR) region for CMC3. Furthermore, chemical oxidations of the N donor sites in CMC1 gave rise to a highly stable radical cation (CMC1·+SbF6-) and diradical dication species (CMC12·2+2SbF6-) that serve as a rare example of a positively charged open-shell chiral macrocycle.

Catalytic Asymmetric Cyclopropanations with Nonstabilized Carbenes.

Cyclopropanes are common building blocks in pharmaceuticals, agrochemicals, and organic materials. The most general methods for the synthesis of chiral cyclopropanes are catalytic additions of diazoalkanes to alkenes. However, a limitation of this approach is that diazoalkanes can only be safely handled on preparative scales if they possess stabilizing substituents. Here we show that gem-dichloroalkanes can serve as precursors to nonstabilized carbenes for asymmetric cyclopropanation reactions of alkenes. The process uses a cobalt catalyst and is proposed to involve the formation of a cationic carbenoid species bearing structural resemblance to the Simmons-Smith reagent. High levels of enantioselectivity are observed for monosubstituted, 1,1-disubstituted, and internal alkenes. The reaction is compatible with alkyl-substituted carbenes, which are susceptible to undergoing competing 1,2-hydride shifts.

Comparative Studies on [B(HFIP)4]-Based Electrolytes with Mono- and Divalent Cations

The development of electrolyte materials that are compatible with reductive metals is an urgent requirement for realizing high-energy-density rechargeable batteries utilizing metallic negative electrodes. Due to successive changes and regeneration of the morphology and fresh metals, respectively, upon repeated cycling of the metallic electrodes, the electrolytes should possess sufficient (electro)chemical stabilities against such electrodes. Weakly coordinating anion (WCA)-based electrolytes, which were first proposed for lithium-based battery applications in 1995, have attracted significant attention, especially in recent years, owing to their successful application in magnesium and calcium metal batteries. Inspired by these studies, WCA-based electrolytes have been reimported into lithium- and sodium-ion battery chemistry. In this study, we conducted comprehensive comparative studies on the representative WCA-based electrolytes incorporating tetrakis(hexafluoro-iso-propoxyl)borate ([B(HFIP)4]−) anions as a model system to understand the effect of valency of paired cation species on transport properties and electrochemical characteristics. As revealed by X-ray crystallography, the monovalent lithium and sodium salts were obtained as adducts, where the anion participated in cation coordination along with a single solvent molecule, whereas divalent magnesium, calcium, and zinc salts formed fully isolated solvates with the divalent cations being coordinated by solvents alone. Such valency-dependent differences in the dissociation states would affect the solution properties, as the divalent electrolytes exhibited greater conductivities than their monovalent counterparts, even though the same number of charged species was present in the respective solutions. The electrochemical metal deposition/dissolution studies combined with morphological and subsequent elemental analysis on the deposits suggested the specific favorable combination of magnesium cations and [B(HFIP)4]− anion in ethereal solutions. The modest surface reactivity of the deposited macrocrystalline magnesium, moderate reductive nature of the magnesium metal, and well-balanced mutual interactions among the components may have jointly contributed to such outstanding performance.

Photoabsorption of Microhydrated Naphthalene and Its Cyano-Substituted Derivatives: Probing Prereactive Models for Photodissociation in Molecular Clouds.

We investigate the photoionization pathways of naphthalene, 1-cyanonaphthalene, and 2-cyanonaphthalene upon complexation with the water dimer, aiming to understand the photodissociation process under conditions of the interstellar medium (ISM). We analyze the intermolecular bonding pattern, equilibrium rotational properties, energy complexation, far-IR spectra, and ionic trends of the possible photoproducts using dispersion-corrected density functional theory (DFT-D) and time-dependent DFT (TD-DFT). For the different configurations, we evaluate the possible charge-transfer (CT) excitations near the photoionization limit. Our results indicate that, in high-radiation regions of the ISM (>8.0 eV), CT excitations occur from localized occupied molecular orbitals (MOs) in the aromatic molecules to mixed unoccupied MOs in the complexes, favoring cationic aromatic species in these conditions. We notice that the photoabsorption spectra depend on the type of intermolecular interaction (H-bonds or O-H···π bonds) in the complexes, as well as the presence and position (1 or 2) of the cyano-functional group in naphthalene. For hydrated naphthalene, the O-H···π complexes assume a more relevant role for photodissociation. In the case of the cyano-substituted derivatives, the H-bonded structures are more favorable to be considered as prereactive models. However, the cyano group at position 2 indicates that CT excitations toward the water dimer are more likely to occur.