Andrés Aracena

A new nitro- and cyano-functionalized, tetradecyl-substituted benzothienoquinolizinium tetrafluoroborate was synthesized through oxidative photocyclisation of a pyridinium precursor and evaluated as a potential small molecule N-type organic semiconductor. The precursor and the photocyclised salts were characterized by UV–Vis absorption spectroscopy, DSC, ¹H and ¹³C NMR, and cyclic voltammetry. Their optoelectronic properties were further investigated by DFT and TD-DFT calculations. Photocyclisation induced a marked bathochromic extension of the absorption profile, decreasing the optical band gap from 3.19 eV for the pyridinium precursor to 2.61 eV for the fused benzothienoquinolizinium salt. Cyclic voltammetry revealed a stabilized electrochemical LUMO level of approximately −3.87 eV, supporting the electron-deficient character of the nitro/cyano-substituted cationic scaffold. Frontier molecular orbital analysis showed that the HOMO and LUMO are mainly localized on the fused π-conjugated core and electron-withdrawing aryl substituents, with negligible contribution from the tetradecyl chain and BF₄⁻ counterion. TD-DFT and electron excitation analyses indicated that the monomeric low-energy transition has mixed local/charge-transfer character, whereas π-stacked dimers, especially the face-to-face arrangement, enhance charge transfer character and reduce electron–hole Coulombic attraction. Marcus type charge transport calculations revealed packing dependent behavior, with the face-to-face dimer displaying nearly ambipolar transport with a slight electron preference. A preliminary theoretical donor–acceptor model with hexaphenyl-substituted hexabenzocoronene further suggested energetic compatibility and strong intermolecular charge-transfer character. Overall, these results identify this benzothienoquinolizinium tetrafluoroborate as a promising electron-deficient cationic π-scaffold for future organic optoelectronic materials.

This study adapted and applied a spatially distributed analytical model to estimate the annual representative leached fraction and the annual potential leached mass of atrazine in the Cauquenes catchment in Chile under contrasting Mediterranean hydroclimatic conditions. The model was based on van der Zee and Boesten and Rakonjac et al. and was modified to account for the strong seasonality of precipitation and evapotranspiration by using representative daily hydrological conditions derived from monthly averages. Spatially distributed soil, climate, land-cover, and atrazine application data were integrated at the pixel scale, including locally corrected soil organic carbon, hydraulic properties, precipitation, evapotranspiration, leaf area index, and annual atrazine dose. The model was applied to two contrasting years, 2018 and 2023, and outputs were aggregated at the pixel, land-cover, hotspot, and catchment scales. The results showed a marked hydroclimatic control on potential atrazine leaching. In the drier year, 2018, both the annual representative leached fraction and the annual potential leached mass were generally very low across the catchment, whereas in the wetter year, 2023, moderate-to-high leaching values became much more spatially extensive, and hotspot areas expanded substantially. At the catchment scale, potential leached mass increased from 0.088 kg in 2018 to 179.784 kg in 2023, while the percentage of applied mass potentially leached increased from 5.50 × 10⁻⁵% to 0.112%. Land-cover classes influenced the results both through the spatial allocation of atrazine application and through LAI-dependent partitioning of evapotranspiration. Global sensitivity analysis using the Morris method identified K_OC and DT50 as the dominant controls on annual potential leached mass, and spatial uncertainty propagation was performed. Overall, the proposed framework provides a potential annual screening estimate and may serve as a preliminary screening tool to prioritize areas for targeted monitoring and future model benchmarking in Chile.

Intensive horticultural and fruit production in Chile relies on pesticides, raising concerns about compliance with residue limits and the continued availability of highly hazardous pesticides (HHPs). Recent national monitoring data from Chile indicate frequent detections of HHPs in plant-based foods and repeated exceedances of Maximum Residue Limits (MRLs). This study analyzed official datasets from Chile’s Ministry of Agriculture, combining food residue monitoring data from 2015 to 2023 with pesticide sales and import statistics as additional indicators of availability. Active ingredients were standardized to ISO names and CAS numbers and classified for HHP status based on FAO/WHO hazard criteria, with cross-referencing to the Pesticide Action Network (PAN). The results present surveillance indicators focusing on detection rates and MRL exceedance proportions. Between 2015 and 2023, residues were identified in 82.8% of the collected samples. The most frequently detected residues overall included fludioxonil, acetamiprid, pyrimethanil, fenhexamid, and boscalid, indicating a detection profile primarily characterized by fungicides with substantial contributions from insecticides. When restricting to HHPs classified residues, the most frequently detected HHPs included tebuconazole, captan, iprodione, spirodiclofen, chlorantraniliprole, and carbendazim, indicating a detection profile primarily characterized by fungicides, with significant contributions from insecticides. Records of exceedances were concentrated within a limited subset of residues, predominantly acetamiprid and dithiocarbonates, and were most frequently associated with apples, table grapes, cherries, blueberries, pears, and certain vegetables, notably leafy vegetables. The active ingredients classified within HHPs included fludioxonil, fenhexamid, tebuconazole, cyprodinil, and lambda-cyhalothrin. The findings support agronomic decision-making by emphasizing GAP/PHI reinforcement, targeted monitoring, and IPM-based substitution options for activities involving recurrent HHP detection.

This work reports the synthesis and characterization of a novel rhenium(I) complex incorporating a phosphorus–nitrogen (P,N) ligand. The compound crystallizes in a distorted octahedral geometry, as confirmed by single-crystal X-ray diffraction analysis. The complexes were evaluated as catalysts in the transfer hydrogenation of acetophenone using 2-propanol as the hydrogen source. Comparative studies with other rhenium(I) complexes bearing polypyridine ligands revealed high catalytic performance, achieving conversions between 68% and 99%. These results highlight the promising potential of P,N-ligand rhenium complexes in homogeneous transfer hydrogenation catalysis. The optimal reaction time was found to be 4 h for the complexes studied, with only the fac-[Re(CO)₃(PN)Cl] complex showing improved conversion upon extending the reaction time to 7 h, likely due to the donor effects provided by the P,N-ligand.

Highly Hazardous Pesticides (HHPs) pose severe risks to human health and the environment, making it essential to understand their molecular stability and degradation pathways. In this study, the Quantum Theory of Atoms in Molecules (QTAIM) was applied to four representative organophosphate pesticides, allowing the identification of electronically weak bonds as intrinsic sites of lability. These findings are consistent with reported hydrolytic, oxidative, enzymatic, and microbial degradation routes. Importantly, QTAIM descriptors proved largely insensitive to solvation, confirming their intrinsic character within the molecular electronic structure. To complement QTAIM, conceptual DFT (Density Functional Theory) reactivity indices were analyzed, revealing that solvent effects induce more noticeable variations in global and local descriptors than in topological parameters. In addition, a Topological Analysis of the Fukui Function (TAFF) was performed, which mapped nucleophilic, electrophilic, and radical susceptibilities directly onto QTAIM basins. The TAFF analysis confirmed that bonds identified as weak by QTAIM (notably P–O, P–S, and P–N linkages) also coincide with the most reactive sites, thereby reinforcing their mechanistic role in degradation pathways. This integrated framework highlights the robustness of QTAIM, the sensitivity of global and local reactivity descriptors to solvation revealed by conceptual DFT, and the complementary insights provided by TAFF, contributing to risk assessment, remediation strategies, and the rational design of safer pesticides.

Polarizable continuum methods (PCM) have been widely employed for simulating solvent effects, in spite of the fact that they either ignore specific interactions in solution or only partially reproduce non-specific contributions. Examples of three solvatochromic dyes with a negative, a positive and a reverse behavior illustrate the achievements and shortcomings of PCM calculations and the causes for their variable success. Even when qualitatively mimicking non-specific solvent effects, departures of calculated values from experimental data may be significant (20–30%). In addition, they can utterly fail to reproduce an inverted behavior that is caused by significant specific contributions by the solvent. As shown through a theoretical model that rationalizes and predicts the solvatochromism of phenolate merocyanines based on DFT (Density Functional Theory) descriptors in the gas phase, PCM shortcomings are to be held responsible for its eventual failure to reproduce experimental data in solution.

Polarizable continuum methods (PCM) have been widely employed for simulating solvent effects, in spite of the fact that they either ignore specific interactions in solution or only partially reproduce non-specific contributions. Examples of three solvatochromic dyes with a negative, a positive and a reverse behavior illustrate the achievements and shortcomings of PCM calculations, and the causes for their variable success. As shown with a theoretical model that rationalizes and predicts the solvatochromism of phenolate merocyanines based on structural parameters, PCM shortcomings are to be held responsible for their eventual failure in reproducing experimental data.

A new benzotrithiophene-based small molecule, namely 2,5,8-Tris[5-(2,2-dicyanovinyl)-2-thienyl]-benzo[1,2-b:3,4-b′:6,5-b″]-trithiophene (DCVT-BTT), was successfully synthesized and subsequently characterized. This compound was found to present an intense absorption band at a wavelength position of ∼544 nm and displayed potentially relevant optoelectronic properties for photovoltaic devices. Theoretical studies demonstrated an interesting behavior of charge transport as electron donor (hole-transporting) active material for heterojunction cells. A preliminary study of small-molecule organic solar cells based on DCVT-BTT (as the P-type organic semiconductor) and phenyl-C61-butyric acid methyl ester (as the N-type organic semiconductor) exhibited a power conversion efficiency of 2.04% at a donor: acceptor weight ratio of 1:1.

Solvatochromic dyes are utilized in various chemical and biological media as chemical sensors. Unfortunately, there is no simple way to predict the type of solvatochromism based on the structure of the dye alone, which restricts their design and synthesis. The most important family of solvatochromic sensors, pyridinium phenolate dyes, has the strongest solvatochromism. Using a natural population analysis (NPA) of the natural bond orbitals (NBO) of the phenolate group in the frontier molecular orbitals, it is possible to calculate the relative polarity of the ground state and excited state and, thus to develop a model that can predict the three types of solvatochromism observed for this family: negative, positive, and inverted. This methodology has been applied to thirteen representative examples from the literature. Our results demonstrate that the difference in the electron density of the phenolate moiety in the frontier molecular orbitals is a simple and inexpensive theoretical indicator for calculating the relative polarity of the ground and excited states of a representative library of pyridinium phenolate sensors, and thus predicting their solvatochromism. Comparing the results with the bond length alternation (BLA) and bond order alternation (BOA) indices showed that the NPA/NBO method is a better way to predict solvatochromic behavior.

Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV–Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.