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In this work, we present the innovative synthesis of salophen (acetaminosalol) derivatives in a solvent-free environment by high-speed ball milling, using a non-conventional activation method, which allowed obtaining compounds in a shorter time and with a better yield. Furthermore, for the first time, the salophen derivatives were deposited as composite films, using a matrix of poly 3,4-ethylene dioxythiophene:polystyrene sulfonate (PEDOT:PSS) polymer. Significant findings include the transformation from the benzoid to the quinoid form of PEDOT post-IPA treatment, as evidenced by Raman spectroscopy. SEM analysis revealed the formation of homogeneous films, and AFM provided insights into the changes in surface roughness and morphology post-IPA treatment, which may be crucial for understanding potential applications in electronics. The optical bandgap ranges between 2.86 and 3.2 eV for PEDOT:PSS-salophen films, placing them as organic semiconductors. The electrical behavior of the PEDOT:PSS-salophen films undergoes a transformation with the increase in voltage, from ohmic to space charge-limited conduction, and subsequently to constant current, with a maximum of 20 mA. These results suggest the possible use of composite films in organic electronics.

RESUMEN

Polymeric hybrid films, for their application in organic electronics, were produced from new ruthenium indanones in poly(methyl methacrylate) (PMMA) by the drop-casting procedure. Initially, the synthesis and structural characterization of the ruthenium complexes were performed, and subsequently, their properties as a potential semiconductor material were explored. Hence hybrid films in ruthenium complexes were deposited using PMMA as a polymeric matrix. The hybrid films were characterized by infrared spectrophotometry and atomic force microscopy. The obtained results confirmed that the presence of the ruthenium complexes enhanced the mechanical properties in addition to increasing the transmittance, favoring the determination of their optical parameters. Both hybrid films exhibited a maximum stress around 10.5 MPa and a Knoop hardness between 2.1 and 18.4. Regarding the optical parameters, the maximum transparency was obtained at wavelengths greater than 590 nm, the optical band gap was in the range of 1.73-2.24 eV, while the Tauc band gap was in the range of 1.68-2.17 eV, and the Urbach energy was between 0.29 and 0.50 eV. Consequently, the above comments are indicative of an adequate semiconductor behavior; hence, the target polymeric hybrid films must be welcomed as convenient candidates as active layers or transparent electrodes in organic electronics.

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We have developed a straightforward and rapid methodology for the synthesis of tetrasubstituted allenes bearing carboxylic acids in the 1,3-position through the gold(I)-catalyzed nucleophilic addition of bis(trimethylsilyl)ketene acetals to ynones. The reaction was evaluated with several substrates, and 21 allenes were obtained in moderate to good yields. Using DFT calculations, we studied the mechanism of the reaction, which suggested a nucleophilic 1,4-addition pathway. The potential of allenes to act as a source of highly functionalized lactones was also explored.

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The chemical doping of silicon phthalocyanine dihydroxide (SiPc(OH)2), with (2E, 4Z)-5, 7-diphenylhepta-2, 4-dien-6-ynoic acids (DAc) with electron-withdrawing (BrDAc) and electron-donating (MeODAc) substituents is the main purpose of this work. Theoretical calculations were carried out on Gaussian16 software, with geometrical optimization of all involved species, and obtention of the highest occupied molecule orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and the respective energy gaps. The theoretical calculations show two hydrogen bridge formations: the first one as a peripheral interaction between the terminal oxygen atoms from the acid unit and hydrogen atoms from the phthalocyanine aromatic rings. The second one as the interaction at the nitrogen atoms of the phthalocyanine, which are compelled to form a new flat plane far from the original flat phthalocyanine deck. These organic semiconductors were deposited as thin films and characterized by IR spectroscopy, atomic force microscopy (AFM), and the optical parameters were gathered from UV-Vis studies. The indirect and direct optical band gap, the onset gap and the Urbach energy were obtained. In order to compare the effect of the acids as dopants of the silicon phthalocyanine, the SiPc(OH)2-DAc films were electrically characterized. The SiPc(OH)2-DAc films exhibit an ambipolar electrical behavior, which is influenced by the incidence of different lighting conditions at voltages above 0.3V. The glass/ITO/SiPc(OH)2-MeODAc/Ag reaches a maximum current of 5.68 × 10-5 A for natural light condition, while the glass/ITO/SiPc(OH)2-BrDAc/Ag, reaches a maximum current of 9.21 × 10-9 A for white illumination condition.

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To aid the possible prevention of multidrug resistance in tumors and cause lower toxicity, a set of sixteen novel dihydropyridine carboxylic acids derivatives 3a-p were produced; thus, the activation of various ynones with triflic anhydride was performed, involving a nucleophilic addition of several bis(trimethylsilyl) ketene acetals, achieving good yields requiring easy workup. The target molecules were unequivocally characterized by common spectroscopic methods. In addition, two of the tested compounds (3a, and 3b) were selected to perform in silico studies due to the highest cytotoxic activity towards the HCT-15 cell line (7.94 ± 1.6 µM and 9.24 ± 0.9 µM, respectively). Employing theoretical calculations with density functional theory (DFT) using the B3LYP/6-311++G(d,p) showed that the molecular parameters correlate adequately with the experimental results. In contrast, predictions employing Osiris Property Explorer showed that compounds 3a and 3b present physicochemical characteristics that would likely make it an orally active drug. Moreover, the performance of Docking studies with proteins related to the apoptosis pathway allowed a proposal of which compounds could interact with PARP-1 protein. Pondering the obtained results (synthesis, in silico, and cytotoxic activity) of the target compounds, they can be judged as suitable antineoplastic agent candidates.

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The hybrid film of molybdenum oxide (MoO3) and poly(3,4-ethylenedyoxithiophene) polystyrene sulfonate (PEDOT:PSS) is a promising candidate for use as hole transport layer (HTL) in low-cost devices. A fast, controllable and economic process was used to fabricate high-performance HTLs by adding organotin (IV) semiconductors to the MoO3/PEDOT:PSS films. These hybrid films were fabricated by spin-coating and the MoO3/PEDOT:PSS-organotin (IV) complex films were characterized by infrared spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). Some mechanical and optical properties of the hybrid films were obtained and, to electrically characterize the hybrid films, hetero-junction glass/ITO/MoO3/PEDOT:PSS-organotin (IV) complex/Ag devices were prepared. Regarding the mechanical properties, the films have high plastic deformation, with a maximum stress of around 40 MPa and a Knoop hardness of 0.14. With respect to optical behavior, the films showed high transparency, with optical gap values between 2.8 and 3.5 eV and an onset gap of around 2.4 eV, typical of semiconductors. Additionally, the films in their respective devices show ambipolar and ohmic behavior with small differences depending on the substituent in organotin (IV) semiconductors. The MoO3/PEDOT:PSS matrix defines the mechanical behavior of the films and the tin complexes contribute their optoelectronic properties.

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Guatemala es un país de gran diversidad biológica, la que ha permitido a diferentes investigadores de productos naturales, obtener resultados de interés y relevancia científica, principalmente sobre propiedades farmacológicas, sin embargo, hasta el momento se desconoce la estructura molecular, conformaciones y configuraciones exactas de muchos de los metabolitos secundarios responsables de dichas propiedades. Por lo tanto, en esta investigación se planteó como objetivo aislar y elucidar la estructura de un fenilpropanoide obtenido en las hojas de Piper patulum. El aislamiento se realizó por extracciones líquido-líquido y técnicas cromatográficas (cromatografía en columna -CC-), obteniendo .092 g del compuesto de interés. La elucidación se realizó por espectroscopía de masas, espectroscopia infrarroja -IR- y experimentos de resonancia magnética nuclear -RMN-, dando como resultado la estructura correspondiente a (E)-1,3,5-trimetoxi-2-(prop-1- enil) benceno. Posteriormente el fenilpropanoide presentó actividad antioxidante mediante la prueba cualitativa con 2,2- difenil-1-picrilhidrazilo -DPPH-.

Guatemala is a country of great biological diversity, which has led natural product researchers to obtain results of great interest and scientific relevance, mainly in pharmacological properties; However, the molecular structure, conformations, and configurations of many secondary metabolites responsible for these properties are unknown. In this research, the objective was to isolate and elucidate the structure of a phenylpropanoid obtained from in the leaves of Piper patulum. The isolation was carried out by liquid-liquid extractions and chromatographic techniques (Column Chromatography -CC-), obtaining .092 g. The elucidation was performed by mass spectroscopy, infrared spectroscopy -IR- and nuclear magnetic resonance experiments-NMR-, the data obtained indicates the corresponding (E) -1,3,5-trimethoxy-2- (prop-1-enyl) benzene. Subsequently, the phenylpropanoid presented antioxidant activity through the qualitative test with 2,2-diphenyl-1-picrylhydrazyl-DPPH

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Chromenes are compounds that may be useful for inhibiting topoisomerase and cytochrome, enzymes involved in the growth of cancer and fungal cells, respectively. The aim of this study was to synthesize a series of some novel 2-amino-3-cyano-4-aryl-6,7-methylendioxy-4H-chromenes 4a-o and 2-amino-3-cyano-5,7-dimethoxy-4-aryl-4H-chromenes 6a-h by a three-component reaction, and test these derivatives for anticancer and antifungal activity. Compounds 4a and 4b were more active than cisplatin (9) and topotecan (7) in SK-LU-1 cells, and more active than 9 in PC-3 cells. An evaluation was also made of the series of compounds 4 and 6 as potential antifungal agents against six Candida strains, finding their MIC50 to be less than or equal to that of fluconazole (8). Molecular docking studies are herein reported, for the interaction of 4 and 6 with topoisomerase IB and the active site of CYP51 of Candida spp. Compounds 4a-o and 6a-h interacted in a similar way as 7 with key amino acids of the active site of topoisomerase IB and showed better binding energy than 8 at the active site of CYP51. Hence, 4a-o and 6a-h are good candidates for further research, having demonstrated their dual inhibition of enzymes that participate in the growth of cancer and fungal cells.

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In this work, we present a comparative study of benzoid poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as electrode and as hole carrier transport layer (HTL) in the manufacture of organic photovoltaic devices using Fischer metal-carbene complexes. The performance of the different devices was evaluated for solar cell applications. Scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the thin films that integrated the devices. A more ordered and crystallized active film microstructure is observed when using benzoid PEDOT:PSS as nucleation layer. The optical gap for both direct and indirect electronic transitions was evaluated from ultraviolet-visible spectroscopy data (UV-vis), as well as the absorption coefficient (α), and the values are in the range of 2.10-2.93 eV. Photovoltaic devices with conventional architecture, using two different chromium carbenes as active layers, were manufactured, and their electrical behavior was studied. The devices were irradiated with different wavelengths between the infrared and ultraviolet regions of the electromagnetic spectrum. Using the PEDOT:PSS film as hole carrier transport layer (HTL) decreases the slope on the ohmic and space charge limited current (SCLC) regions and eliminates the trap-charge limited current (T-CLC) mechanism. Furthermore, a saturation current of ~1.95 × 10-10 A and higher current values ~1.75 × 10-2 A at 4 V, ~4 orders in magnitude larger were observed. The PEDOT:PSS films as HTL in the devices reduced the injection barrier, thus showing a better performance than as anodes in this type of organic solar cells.

RESUMEN

A new series of Fischer carbenes have been synthetized and examined as hole-transporting or electron-transporting layers (HTLs or ETLs) in the fabrication of organic solar cells (OSCs). The synthesis of three Fischer aminocarbene complexes with the general formula [Cr(CO)5{C(NHCH2)Ar}] (Ar = 2-pyridyl (3a), 3-pyridyl (3b) and 4-pyridyl (3c)) is reported. The molecular structure of complex 3b has been confirmed by X-ray analysis. In order to study the possible applications of the three Fischer aminocarbenes in OSCs, thin films of these complexes were prepared using a vacuum deposition process. These organometallic films were chemically and morphologically characterized by IR spectroscopy, SEM, AFM and XRD. According to the IR and Tauc analysis, the vacuum deposition process generates thin films free of impurities with an activation energy of 4.0, 2.7 and 2.1 eV for 3a, 3b y 3c, respectively. The UV-vis spectra of the amorphous aminocarbene films show that they are practically transparent to the visible radiation of the electromagnetic spectrum. This is due to the fact that their absorption is located mainly in the ultraviolet range. Two OSCs with bulk-heterojunction configuration were manufactured in order to prove the use of the aminocarbenes as ETL o HTL. The aminocarbene [Cr(CO)5{C(NHCH2) 4-pyridyl}] (3c) proved to be suitable as ETL with a fill factor (FF) of 0.23 and a short circuit current density (JSC) of 1.037 mA/cm².

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A series of 3-benzoyl imidazo[1,2-a]pyrimidines, obtained from N-heteroarylformamidines in good yields, was tested in silico and in vitro for binding and inhibition of seven Candida species (Candida albicans (ATCC 10231), Candida dubliniensis (CD36), Candida glabrata (CBS138), Candida guilliermondii (ATCC 6260), Candida kefyr, Candida krusei (ATCC 6358) and Candida tropicalis (MYA-3404)). To predict binding mode and energy, each compound was docked in the active site of the lanosterol 14α-demethylase enzyme (CYP51), essential for fungal growth of Candida species. Antimycotic activity was evaluated as the 50% minimum inhibitory concentration (MIC50) for the test compounds and two reference drugs, ketoconazole and fluconazole. All test compounds had a better binding energy (range: -6.11 to -9.43 kcal/mol) than that found for the reference drugs (range: 48.93 to -6.16 kcal/mol). In general, the test compounds showed greater inhibitory activity of yeast growth than the reference drugs. Compounds 4j and 4f were the most active, indicating an important role in biological activity for the benzene ring with electron-withdrawing substituents. These compounds show the best MIC50 against C. guilliermondii and C. glabrata, respectively. The current findings suggest that the 3-benzoyl imidazo[1,2-a]pyrimidine derivatives, herein synthesized by an accessible methodology, are potential antifungal drugs.

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We report a one-pot synthesis of chiral ß2,2,3-amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure ß-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

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The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO)5NH(CH2)15CH3, where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir-Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

RESUMEN

Multicomponent reactions are excellent methods that meet the requirements of green chemistry, by reducing the number of steps, and consequently reducing purification requirements. Accordingly, in this work, 11 novel hybrid-boron-containing molecules, namely eight 1,4-dihydropyridines and three 3,4-dihydropyrimidinones, derived from formylphenylboronic acids (ortho, meta and para), were obtained using a green approach, involving H-4CR and B-3CR practices, in the presence of ethanol, which is a green solvent, and using three comparatively different modes of activation (mantle heating, yield 3%-7% in 24 h, Infrared Radiation (IR) irradiation, yield 12%-17% in 12 h, and microwave irradiation, yield 18%-80%, requiring very low reaction times of 0.25-0.33 h). In addition, as a green-approach is offered, a convenient analysis, of the 12 green chemistry principles for the overall procedure was performed. Finally, since all the products are new, characterizations were carried out using common analytic procedures (1H, 11B, and 13C NMR, FAB+MS, HRMS, and IR). The accurate mass data of unexpected ions related to interactions between thioglycerol and the expected products, in the FAB+-mode, enabled unequivocal characterization of the target molecules.

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We report the synthesis of new copper(I) complexes 6a-e from methyl 3-hydroxy-3-(p-R-phenyl)-2-propenedithioate ligands. These complexes were characterized by IR and 1H, 13C, and 31P NMR spectroscopy. The expected O,S-coordination mode was confirmed by the X-ray diffraction studies of 6b and 6e. The unexpected dimerization of 6b-e leads to the formation of four novel dinuclear copper(I) compounds (7b-e). The dinuclear complex structure was fully established by the X-ray diffraction analysis of 7a, in which the presence of a Cu-Cu interaction was observed.

RESUMEN

New complexes of the pinch-porphyrin family were obtained from the dimethylester of (proto-, meso-, and deutero-porphyrinato)iron(III) with the ligand [N,N'-bis-pyridin-2-ylmethyl-propane-1,3-diamine] 1-3 and with the ligand [N-pyridin-2-ylmethyl-N'-[3-[(pyridin-2-ylmethyl)-amino]-propyl]-propane-1,3-diamine] 4-6. The UV/VIS studies of 1-6 indicate an increase in the distortion of the ligand field excited state. The 1H NMR spectra of 1-6 at RT and over the range 223-328 K show iron(III)-complexes with quantum mixed spin state (qms) S=5/2, S=3/2. The chemical shifts of the meso protons are consistent with qms state S=3/2, S=5/2, where the S=3/2 spin state is lowest in energy. For methyl-heme the chemical shifts are also consistent with a qms state but now the S=5/2 ground state is lowest in energy. ESR spectra of 1-6 show two different species, B and C, of iron(III) with qms, S=5/2, S=3/2 consistent with the 1H NMR results. Species B with 70% of S=5/2 and species C with 72.5% of S=3/2. The catalytic activity as peroxidase of 1-6 was quantified by guaiacol test; their theoretical maximum rate constants were k(cat) approximately 10(2)-10(3) M(-1) s(-1). A quantitative empirical correlation is found: the higher the 32 spin contribution to the qms state and the higher proportion of this species into the samples, the higher the peroxidase activity. Such a correlation was also obtained for pinch-porphyrins already reported.

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