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Wittig olefination at hetero-benzylic positions for electron-deficient and electron-rich heterocycles has been studied. The electronic effects of some commonly used protective groups associated with the N-heterocycles were also investigated for alkenes obtained in the context of the widely employed Wittig olefination reaction. It was observed that hetero-benzylic positions of the pyridine, thiophene and furan derivatives were stable after Wittig olefination. Similarly, electron-withdrawing groups (EWGs) attached to N-heterocycles (indole and pyrrole derivatives) directly enhanced the stability of the benzylic position during and after Wittig olefination, resulting in the formation of stable alkenes. Conversely, electron-donating group (EDG)-associated N-heterocycles boosted the reactivity of benzylic alkene, leading to lower yields or decomposition of the olefination products.

The photoinduced solid-to-liquid transitions property of azobenzene-containing polymers (azopolymers) enables azopolymers with various promising applications. However, a general lack of knowledge regarding the influence of structure of the azobenzene derivatives on the photoinduced liquefaction hinders the design of novel azopolymers. In the present study, a series of azopolymers with side chains containing azobenzene unit bearing alkyl electron-donating groups were synthesized. The photoisomerization and photoinduced liquefaction properties of newly synthesized azopolymers were investigated. Alkyl-based electron-donating group significantly facilitate the photoisomerization process of azopolymers in solution, as the electron-donating ability of substituents increased, the time required for photoisomerization of azopolymers continually deceased. Meanwhile, the electron-donating group can drastically accelerate photoinduced solid-to-liquid transitions of azopolymers, the liquefaction rate of obtained azopolymers gradually getting quicker as the electron-donating ability of substituents increased. This study clearly demonstrates that the electron-donating group that bearing in the azobenzene group of polymer side chain play an essential role on the photoinduced solid-to-liquid transitions of azopolymers, and hence, gives an insight into how to design novel azopolymers for practical applications.

Heterocyclic compounds have shown that they hold significant therapeutic activities, highlighting the importance of discovering and developing novel candidates against cancers, infections, and oxidative stress-associated disorders. In this study, we demonstrated the biological activity of our previously synthesized thiazolidinone derivatives (TZDs-1, 6, and 7). Furthermore, we synthesized and structurally characterized a new derivative (TZD-5) using IR, 1H NMR, and 13C NMR spectroscopy, confirming the presence of its key functional groups, namely, carbonyl and imine. Their antioxidant activity was assessed through the DPPH assay, with TZD-5 showing the most potent effect (IC50 = 24.4 µg/mL), comparable to ascorbic acid, an effect attributed to the methoxy group introduced via N-alkylation. Cytotoxicity was evaluated using the MTS assay on normal (HFF-1) and cancerous (HepG2 and A549) cell lines at two time points: 24- and 48 h exposure. Our findings highlight clear differences in cytotoxicity and selectivity among the tested thiazolidinone derivatives. TZD-1 and TZD-6 demonstrated significant, dose-dependent cytotoxic effects on both cancerous (HepG2 and A549) and normal (HFF-1) cell lines, thus limiting their therapeutic potential due to insufficient selectivity. TZD-5 exhibited moderate selectivity with higher susceptibility for HepG2 cells compared to normal cells. Notably, TZD-7 showed the most favorable cytotoxic profile, demonstrating strong selective cytotoxicity toward cancer cell lines with minimal adverse effects on normal fibroblasts. Overall, the results highlight TZD-5 and TZD-7 as promising candidates for antioxidant and selective anticancer therapies.

The photophysical properties of closo-ortho-carboranyl-based donor–acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of 1F and 4T were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π–π* transition of the 9-phenyl-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λem = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S1) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for 1F < ‒H for 2P < ‒CH3 for 3M < ‒C(CH3)3 for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.

Chalcones are a class of compounds which are naturally occurring and can be synthetically accessed as well. Due to their versatile properties and nature, they are not limited to pharmaceutical applications but then they extend their potential in other various fields of chemistry including material science. As the presence of this core has been very much prominent in different areas of material chemistry, herein, this review highlights the application of chalcones and their derivatives in the field of non-linear optics, polymer, and corrosion inhibiton. The presence of α–β unsaturated carbonyl group enables chalcone moiety to function efficiently as corrosion inhibitors. In addition, the carbonyl group being in conjugation with the donor and acceptor groups have made the chalcone moiety to exhibit significant Non-Linear optical properties (NLO) as well. Chalcones based polymers have applications in material science due to their properties such as optical, mechanical and thermal characteristics, making them an important class of compounds. Hence this review provides the literature on these three applications thus affording ideas to design the new molecules containing chalcones as the main core.Article highlightsApplications of chalcones and its derivatives in corrosion inhibition, Non-Linear Optical studies and polymers.Brief explanation on role of various substituents attached to the chalcone moiety.Discussion of structure-property relationship for designing new chalcone containing scaffolds.

Context The world’s energy and environmental requirements are changing due to rapid population growth and industrial growth, and solar cells can be used to meet these demands. Dye-sensitized solar cells (DSSCs) are solar cells in which energy conversion occurs via a process similar to photosynthesis in plants. DSSC development is still in its infancy. DSSCs can operate under cloudy conditions and indirect sunlight and have attracted considerable attention due to their low cost and high efficiency. We designed two metal-free TPA-based dyes (Dye2 and Dye3) based on the reference dye Mg207 (Dye1) by increasing the donor strength of the molecule, as such dyes have shown enhanced efficiency in DSSCs. Moreover, the triphenylamine (TPA) moiety has been demonstrated to be a good donor that prevents charge recombination. Intramolecular charge transfer (ICT) from the donor to acceptor moiety was found in the sensitizers, and electrons were promoted to the conduction band (CB) of the TiO 2 semiconductor. The negative binding energy of the dye@TiO 2 clusters indicated that dye adsorption on the semiconductor surface was stable. The double donor increased the electron injection and electronic coupling constants in Dye2 and Dye3, indicating that these newly designed dyes have superior charge injection capacity. Accordingly, the efficiencies of DSSCs with Dye2 and Dye3 were 9.77% and 9.62%, respectively, and substitution with the TPA unit at the -R1 and -R2 positions in Dye1 resulted in better power conversion compared to the parent compound (9.09%). Increased donor strength improved photovoltaic performance by increasing current density and light-harvesting efficiency. This is a good molecular design approach for preparing targeted donor- π -acceptor (D- π -A) organic dyes with high DSSC efficiency. Methods To predict the charge transport and optoelectronic characteristics of the TPA dyes, quantum chemical calculations were carried out using Gaussian16. The ground-state ( S 0 ) optimized geometries of the sensitizers were computed by utilizing DFT at the B3LYP/6-31G** level. The absorption spectra ( λ max ) were computed by employing TD-DFT with various functionals (B3LYP, PBE1PBE, CAM-B3LYP, and BHandHLYP) in the gas and solvent (DCM) phases. Among the studied functionals, BHandHLYP was found to be best at successfully reproducing the experimental data. Thus, the absorption spectra of the newly designed dyes and dye@TiO 2 were calculated at the BHandHLYP/6-31G** level. The dye@TiO 2 cluster optimizations were carried out at the B3LYP/6-31G**(LANL2DZ) level.

The effect of electron-donating and electron-withdrawing groups grafted onto polyethylene on electron mobility was studied using density functional theory. In order to ensure the accuracy of the calculation results, 17 basis sets from six methods were screened. 3-methylpentane was selected as the cross-linked polyethylene model. Compared with the experimental values, the theoretical calculation results show that wB97XD/6-311G(d,p) is more suitable for studying the electron mobility system. The roles of electron-donating and electron-withdrawing functional groups were studied. The results show that the electron mobility of grafting nitrobenzene (Ebnb) to polyethylene is the smallest among the studied molecules. As the ability of electron-donating groups increases, the electron mobility gradually increases, while the addition of the electron-withdrawing group reduces the electron mobility and the electron mobility gradually increases with increasing temperature. This investigation is expected to provide reliable information for the development of insulation materials for cables.

p-Benzoquinone (BQ) is a promising candidate for next-generation sodium-ion batteries (SIBs) because of its high theoretical specific capacity, good reaction reversibility, and high resource availability. However, practical application of BQ faces many challenges, such as a low discharge plateau (∼2.7 V) as cathode material or a high discharge plateau as anode material compared with inorganic materials for SIBs and high solubility in organic electrolytes, resulting in low power and energy densities. Here, tetrahydroxybenzoquinone tetrasodium salt (Na 4 C 6 O 6 ) is synthesized through a simple neutralization reaction at low temperatures. The four −ONa electron-donating groups introduced on the structure of BQ greatly lower the discharge plateau by over 1.4 V from ∼2.70 V to ∼1.26 V, which can change BQ from cathode to anode material for SIBs. At the same time, the addition of four −ONa hydrophilic groups inhibits the dissolution of BQ in the organic electrolyte to a certain extent. As a result, Na 4 C 6 O 6 as the anode displays a moderate discharge capacity and cycling performance at an average work voltage of ∼1.26 V versus Na/Na + . When evaluated as a Na-ion full cell (NIFC), a Na 3 V 2 (PO 4 ) 3 ‖ Na 4 C 6 O 6 NIFC reveals a moderate discharge capacity and an average discharge plateau of ∼1.4 V. This research offers a new molecular structure design strategy for reducing the discharge plateau and simultaneously restraining the dissolution of organic electrode materials.

A series of porphyrin compounds, free base (H2P) and their Zn (II) metallated analogues (ZnP), bearing one, two or three carboxylic acid groups, have been synthesized, characterized, and used as sensitizers in dye sensitized solar cells (DSSCs). The performance of these devices has been analyzed, showing higher efficiencies of those sensitized with ZnP compounds. These results have been explained, on one hand, taking into account the electronic character of the metal ion, which acts as mediator in the injection step, and, on the other, considering the number of anchoring groups, which determines both the stereoelectronic character of the dye and the way it binds to TiO2 surface.