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We designed six 4,6-di(pentacenothiophene-2-yl)pyrimidine molecules with excellent charge transport properties. The optimization of ground-state geometries with B3LYP/6-31G** level is adopted with the help of first-principle investigations. The bridge elongation strategy was employed to strengthen intra-molecular charge transfer. The time-dependent density functional theory (TDDFT) was employed for the measurement of absorption spectra (λabs). The λabs, energy gaps (Egaps), frontier molecular orbitals (FMOs) energies, electron injection, ionization energy (IE), electron affinity (EA) along with reorganization energy (λ) values were computed. The substitution of long-chain polyacene cores as well as thiophene enhanced the EA, reduces hole/electron λ along with their IE. The λ(h), and λ(e), were compared with hole and electron transfer within mostly used compounds, like pentacene and tris(8-hydroxyquinolinato)aluminum (mer-Alq3), respectively. It is anticipated that novel designed compounds may be better to be used for hole transfer (as pentacene) and electron transfer (as mer-Alq3) compounds. These derivatives would act as productive materials that can be employed as p- and n-type semiconductors. The elongation of oligothiophene and acene cores act as excellent hole transfer materials that may be better than frequently used p-type reference compounds. These designed derivative also showed lower λ (e) values exhibited that these may be best/comparable with commonly used n-type mer-Alq3. [ABSTRACT FROM AUTHOR]

Due to the increasing demand of Al 1 2 N 1 2 in optoelectronics and sensing materials, we intended to investigate the adsorption behavior, electronic nature and NLO response of hydrogen and different metals decorated Al 1 2 N 1 2 nanocages. Different systems are designed by hydrogen adsorption and encapsulation of metals (Li, Na and K) in Al 1 2 N 1 2 . Density functional theory at B3LYP functional with conjunction of 6-31G(d , p) basis set is utilized in order to gain optimized geometries. Different calculations including linear and first-order hyperpolarizability are conducted at same level of theory. Instead of chemiosorption, a phyisosorption phenomenon is seen in all hydrogen adsorbed metal encapsulated Al 1 2 N 1 2 nanoclusters. The Q NBO analysis confirmed the charge separation in hydrogen adsorbed metal encapsulated nanocages. Molecular electrostatic potential (MEP) analysis cleared the different charge sites in all the systems. Similarly, frontier molecular orbitals analysis corroborated the charge densities shifting upon hydrogen adsorption on metal encapsulated AlN nanocages. HOMO–LUMO band gaps suggest effective use of H2-M-AlN in sensing materials. Global indices of reactivity also endorsed that all hydrogen adsorbed metal encapsulated systems are better materials than pure Al 1 2 N 1 2 nanocage for sensing applications. Lastly, linear and first hyperpolarizability of H2-M-AlN nanocages are found to be greater than M-AlN and pure AlN nanocages. Results of these parameters recommend metal encapsulated nanocages as efficient contributors for the applications in hydrogen sensing and optoelectronic devices. NLO response along with electronic properties of metal encapsulated Al12N12 nanocages were explored followed by hydrogen adsorbed metal encapsulated Al12N12 nanocages. Results of these parameters recommend metal encapsulated nanocages as efficient contributor for possible applications in hydrogen sensors materials and in optoelectronic materials. [ABSTRACT FROM AUTHOR]

Charge transport and electronic character of fluorophore chalcogenides 4,4-Difluoro-8-(-XC4H3)-4-bora-3a,4a-diaza-s-indacene (X = O, S, Se) (BODIPY) derivatives were examined at the molecular level. The effect of chalcogenides was investigated on the transfer integrals, electron affinity (EA), frontier molecular orbitals (FMO), ionisation energy (IE), intrinsic mobility along with reorganisation energies. The ring dissimilarities within 4,4-difluoro-8-(-XC4H3)-4-bora-3a,4a-diaza-s-indacene (X = O, 2-/3-furyl (Comp1/Comp4)); (X = S, 2-/3-thienyl (Comp2/Comp4)) and (X = Se, 2-/3-selenenyl (Comp3/Comp6)) were compared systematically. Among BODIPY chalcogenides derivatives, 2-furyl substitution is more beneficial compared with 2-thienyl, 2-selenenyl and 3-furyl as the prior moiety significantly increases intrinsic hole mobility. The –S or –Se substitution at 2- or 3- position in place of –O at equivalent position reduces the structural polarisation from neutral to cation resulting in reduced hole reorganisation energies. The doping of –S or –Se at 2-position decreases the hole transfer integral in comparison to 2-furyl-substituted derivative. The effect of chalcogen atoms on 2- or 3- position is not so significant on the HOMO/LUMO energy levels. It is expected that –O doping at 2-position in furyl is supporting p-type charge transport channel. These results demonstrated that the studied BODIPY derivatives would be efficient hole transfer materials to be used in organic semiconductor devices. [ABSTRACT FROM AUTHOR]

New cytotoxic steroidal glycoside of methanol extract from Kochia prostrata (L.) Schrad was investigated in this study. Bio-guided isolation from ethylacetate fraction of whole plant afforded steroidal glycosides named as 5-ene-dimethylcholest3-O- β -D-glucoside (Kochioside 1A1), 5-ene-methylcholest3-O- β -D-glucoside (Kochioside 2A1) and 4-ene-dimethylcholest3-O- β -D-glucoside (Kochioside 3A1). Their structures were assigned by physical and spectroscopic methods. Kochiosides 1A1–3A1 showed inhibitory potential against brine shrimp lethality bioassay with etoposide standard drug. The new steroidal glycoside kochiosides 1A1–3A1 showed inhibition values of 8.3201, 8.8205 and 8.2310 μ g/mL, respectively with LD 5 0 compared to standard etoposide LD 5 0 (7.4625 μ g/mL) drug. Moreover, six new derivatives were designed by substituting the –NH2 and –OCH3 at R1, R2 and R3 positions in the isolated compounds. Herein, various molecular descriptors, frontier molecular orbitals (FMO), electron affinity, ionization potential and molecular electrostatic potential (MEP) were carried out to understand the active sites and biological active nature of the new cytotoxic steroidal glycoside kochiosides. The effect of electron donating groups (–NH2 and –OCH3) was also investigated on the structural parameters and electronic properties in gas and solvent (DMSO) phases. The energy gap, MEP and reactivity descriptors values demonstrate that the kochioside 3A1 retains good reactivity, which is in good agreement with current experimental studies. New cytotoxic steroidal glycoside of methanol extract from Kochia prostrata (L.) Schrad was investigated. Moreover, six new derivatives were designed by substituting the –NH2 and OCH3 at R1, R2 and R3 positions. The effect of electron donating groups (–NH2 and –OCH3) were also investigated on the structural parameters and electronic properties in gas and solvent (DMSO) phases. The energy gap, molecular electrostatic potential and reactivity descriptors values demonstrate that the kochioside 3A1 retains good reactivity, which is in good agreement with current experimental studies. [ABSTRACT FROM AUTHOR]

• Electronic and charge transport nature of 10-(1,3-Dithiol-2-ylidene)anthracene based OSMs was explored. • Effect of bridge and anchoring group was probed on intrinsic mobility. • p - or n -type charge transport ability was systematically probed. • 3,4-ethylenedioxythiophene bridge would be decent to design p -type materials. • Dicyanovinylene might be a good for designing n -type semiconductors. Electronic and charge transport nature of 10-(1,3-Dithiol-2-ylidene)anthracene based organic semiconductor materials (OSMs) have been explored at the molecular level. Effect of phenyl and 3,4-ethylenedioxythiophene of conjugated π-bridge and electron anchoring groups (−CHO and dicyanovinylene) was explored on various properties. The dicyanovinylene group lead to diminish electron reorganization energies while 3,4-ethylenedioxythiophene moiety enhance the hole transfer integrals. The dicyanovinylene groups along with 3,4-ethylenedioxythiophene moiety is favouring to reduce the HOMO and LUMO energy levels as well as their energy gap. The 3,4-ethylenedioxythiophene as bridge in OSMs would be decent to design p -type semiconductors. It is anticipated that dicyanovinylene as anchoring group might be a good approach for designing n -type semiconductors. The p - or n -type charge transport ability of anthracene derivatives was probed here. The transfer integrals, frontier molecular orbitals (FMO), ionization energy (IE), electron affinity (EA), reorganization energy, and intrinsic mobility showed that anthracene based derivatives might be proficient competitors to be applied in semiconductor devices. [ABSTRACT FROM AUTHOR]

Keeping in view the therapeutic importance of ureases due to its involvement in different pathological conditions, its inhibition was investigated by newly synthesized benzenesulfonohydrazides. Elemental analysis, IR, 1H NMR and 13C NMR spectral studies were performed to elucidate the structure of benzenesulfonohydrazides. In vitro urease enzyme inhibition assay revealed the compound INS-5 was found to be the most potent (IC 50 = 1.11 ± 0.29 μM) among the tested compounds. The compound INS-2 was competitive inhibitor with Ki value 5.60 μM while the compounds INS-1 and INS-5 were mixed type of inhibitors with Ki values 4.32 and 2.76 μM respectively. Ancillary to synthetic studies, DFT and TDDFT calculations at B3LYP/6-311G(d,p) level of theory were performed for comparative analysis of spectroscopic data, frontier molecular orbitals (FMOs), natural bond orbital (NBO) analysis and molecule electrostatic potential (MEP) surface. Overall, experimental findings were supported nicely by corresponding DFT computed results. The NBO analysis confirmed that the presence of hyperconjugative interactions are pivotal cause for stability of investigated compounds. Global reactivity descriptors were also calculated using the energies of FMOs energies. Molecular docking studies were performed to identify the plausible binding mode of the competitive inhibitor. Image 1 • New Benzenesulfonohydrazide were synthesized and urease enzyme inhibition was evaluated through in vitro assays. • All compounds displayed potent urease inhibitory activity with IC 50 values of 1.11–4.89 μM. • Compound INS-2 was competitive inhibitor with Ki values 5.60 µM. • Molecular docking studies were established to elucidate the binding energy and interaction. • DFT and TDDFT calculations at B3LYP/6-311G(d,p) level of theory were performed, overall, experimental findings were supported nicely by corresponding DFT computed results. [ABSTRACT FROM AUTHOR]

• Phytochemical investigations from ethanolic extract of Oxalis corniculata L. • Bio-guided fractionation showed high phenolic and flavonoid contents. • Significant carbonic anhydrase, cholinesterase (AChE, BChE) inhibitions were probed. • The electronic properties, molecular descriptors and Hirshfeld charges were studied. Phytochemical investigations of Oxalis corniculata L. shown the existence of biologically active secondary metabolites like phenols, flavanoids, alkaloids, tannins, triterpenes, sterols, and volatile oils. In this work, ethanolic extract of Oxalis corniculata L. was prepared to explore the carbonic anhydrase and cholinesterase inhibitory activities against epilepsy and anti-Alzheimer's disease (AD) potential. Upon fractionation, chloroform and ethyl acetate fractions showed high phenolic (168.56 and 171.11 μ g ascorbic acid/g extract) and flavonoid contents (115.72 and 99.35 μ g (+)-catechin/g extract), respectively and were the most active ones against acetylcholinesterase (AChE), butyrylcholinesterase (BChE) and carbonic anhydrase inhibition. The bioactivity-guided isolation from chloroform and ethyl acetate extract of Oxalis corniculata afforded nine flavonoids. The newly isolated flavonoid (1) and eight source compounds 2–9 screened by cholinesterase (AChE and BChE) and carbonic anhydrase-II (CA-II) inhibitory assays. Carbonic anhydrase inhibition rate for compounds 1–9 ranged 65.21–90.82 with the IC 50 17.11–25.18, compared with reference acetazolamide. Cholinesterase (AChE and BChE) inhibitory potential (49.52 and 29.12 μ g/mL) of newly isolated compound 1 whereas compounds 3 , 5 , 8 and 9 showed considerable significant inhibition potential using standard inhibitor serine. Moreover, the ground state geometries of all the nine compounds along with positive drugs were optimized by Density functional theory (DFT) at B3LYP/TZ2P level to explore the electronic properties and active sites. The effect of substituents on the molecular descriptors, frontier molecular orbitals, molecular electrostatic potential and Hirshfeld charges was explored. [ABSTRACT FROM AUTHOR]

Researchers are presently concentrating on utilization of fullerene-free organic chromophores as efficient materials for solar cells to align with the demands of modern technology. Keeping in view the importance of non-fullerene, a group of V-shape naphthalene diimide-based chromophores (MBPV1 - MBPV5) for OSCs with A 2 – π – A 1 – D – π – A 2 framework were designed by modifying their π -spacer and A 1 acceptor. Analyses like absorption properties (UV-Vis), open circuit voltage (V oc), frontier molecular orbital (FMOs), transition density matrix (TDM), the density of state (DOS), and power conversion efficiencies (PCEs) were executed at MPW1PW91/6–31(d,p) functional, to study the key electronic properties of the naphthalene based compounds. Structural modeling with π-spacer and acceptor moieties causes a reduction in band gap with broader absorption spectra particularly in MBPV4 (ΔE = 2.011 eV and λ max =682.996 nm). An effective transfer of charge towards LUMO from HOMO orbital was studied which was further supported by DOS and TDMs heat maps. Further, open circuit voltage (V oc) analysis was performed with respect of HOMO P3HT -LUMO acceptor and among all the tailored chromophore, MBPV4 exhibited a significant V oc value: 2.296 V with a power conversion efficiency of 31.96%. The designed chromophores demonstrated favorable optoelectronic behavior. Hence, this research illustrates that the engineered chromophores with electron withdrawing units may offer a favorable option for constructing advanced organic solar cells in upcoming applications. [Display omitted] • Designing of naphthalene diimide based chromophores for OSCs. • Structural modeling with π -spacer and acceptor moieties. • Exploration of photovoltaic behavior of designed chromophores. • Study of key electronic properties at MPW1PW91/6-31 G (d,p) functional. • Utilization of TD-DFT approach for FMOs and UV-Vis analyses. [ABSTRACT FROM AUTHOR]

The new design of 6,6′-di(thiophen-2-yl)-4,4′-bipyrimidine (DTB)-based organic dyes (TCIT1-TCIT6) for dye-sensitized solar cell (DSSC) application was systematically designed by a donor (D), π-linker, and acceptor (A) design to form the D-π-D-π-A structure. The exchange–correlation (XC) as well as long-range corrected (LC) functionals were utilized to represent these dyes in density functional theory (DFT) and time-dependent DFT (TD-DFT) techniques. The TD-CAM-B3LYP approach was perfectly matched the DTB dye. Energy gaps between highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) ranged between 1.73-2.92 eV. Their light-harvesting efficiency (LHE) values ranged between 0.001-0.106 eV with dye TCIT5 with the highest value. The open circuit voltage calculated against the DTB as donor moiety ranged 2.45–3.64 eV with positive values to demonstrate their ON position in their solar devices. All the dyes showed a very short excited-state lifetime ranging between 0.0001-0.0051 ns which showed how easily they can shift from an excited- (fluorescent) to ground-state position. Improved results for DSSCs were provided by the intended dyes in addition to their high horizontal dipole moment (µnormal) and open circuit photovoltage (eVOC). It benefits increased efficiency as a result. The findings of the current theoretical analysis show that all D-π-D-π-A dyes may be suitable sensitizers for DSSC applicability. [ABSTRACT FROM AUTHOR]

Considering the increased demand and potential of photovoltaic devices in clean, renewable electrical and hi-tech applications, non-fullerene acceptor (NFA) chromophores have gained significant attention. Herein, six novel NFA molecules IBRD1–IBRD6 have been designed by structural modification of the terminal moieties from experimentally synthesized A2-A1-D-A1-A2 architecture IBR for better integration in organic solar cells (OSCs). To exploit the electronic, photophysical and photovoltaic behavior, density functional theory/time dependent-density functional theory (DFT/TD-DFT) computations were performed at M06/6-311G(d,p) functional. The geometry, electrical and optical properties of the designed acceptor molecules were compared with reported IBR architecture. Interestingly, a reduction in bandgap (2.528–2.126 eV), with a broader absorption spectrum, was studied in IBR derivatives (2.734 eV). Additionally, frontier molecular orbital findings revealed an excellent transfer of charge from donor to terminal acceptors and the central indenoindene-core was considered responsible for the charge transfer. Among all the chromophores, IBRD3 manifested the lowest energy gap (2.126 eV) with higher λmax at 734 and 745 nm in gaseous phase and solvent (chloroform), respectively due to the strong electron-withdrawing effect of five end-capped cyano groups present on the terminal acceptor. The transition density matrix map revealed an excellent charge transfer from donor to terminal acceptors. Further, to investigate the charge transfer and open-circuit voltage (Voc), PBDBT donor polymer was blended with acceptor chromophores, and a significant Voc (0.696–1.854 V) was observed. Intriguingly, all compounds exhibited lower reorganization and binding energy with a higher exciton dissociation in an excited state. This investigation indicates that these designed chromophores can serve as excellent electron acceptor molecules in organic solar cells (OSCs) that make them attractive candidates for the development of scalable and inexpensive optoelectronic devices. [ABSTRACT FROM AUTHOR]

New organic dyes (H1-H6) for their promising applications as dye sensitized solar cell (DSSCs) were theoretically designed from 6,6′-di(thiophen-2-yl)-4,4′-bipyrimidine (TB) moiety in acceptor (A), π-spacer, and donor (D) type architecture to create A-π-D-π-D-π-A framework. After their benchmarking study against various exchange correlation (XC) and long-range corrected (LC) functional, the CAM-B3LYP produced accurate results so as selected for further density functional theory (DFT) and time dependent DFT (TD-DFT) studies. The frontier molecular orbitals (FMOs) were analyzed for their electron transfer properties, and their energies of the highest occupied molecular orbital (EHOMO) and the lowest unoccupied molecular orbital (ELUMO) were used to assess various electronic properties. Their energy differences (EH-L) ranged between 1.69 and 2.03 eV indicating their good responsiveness to electron injection (Ginj) being the values greater than 0.2 eV. The maximum absorbance of the dyes was reported around the 388–406 nm while their starting material (TB) had this value to be 371 nm. This redshift was significant with an intensification of electron-withdrawing groups on the dye structures. The dyes were evaluated for their device related parameters like their light harvesting efficiency, open circuit voltage, exciton binding energies, and exciton life times which were found in their promising values. The dyes were analyzed for their linear (α), first (βtotal), and second (γtotal) order nonlinear responses and were found to have significantly higher responses, not only against their starting materials but also those reported in literature for standard molecules (urea and p-nitric acid). Among the dyes under study, dye H4 exhibits the highest molecular polarizability (α) and hyperpolarizability (β and γ) values thanks to two CN substituted units on each ends. These dyes are most likely to have possible optical and photonic uses. Also, according to the results of the current theoretical research, all of these dyes may function as effective photosensitizer for their DSSC application. [ABSTRACT FROM AUTHOR]

Thiosemicarbazones are considered as emerging scaffolds for various research domains due to their diverse applications. Herein, novel thiosemicarbazone based compounds 1–5 were derived from the condensation reaction between salicylaldehyde and differently substituted thiosemicarbazides with an excellent yield. The structures of yielded chromophores have been confirmed by UV–Vis, vibrational (IR) and NMR spectral techniques. Besides this, DFT study was also accomplished to elucidate the electronic properties of 1–5 chromophores at M06/6-311G(d,p) level. Different kind of investigation: natural bond orbital (NBO), natural population analysis (NPA), frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) and global reactivity parameters (GRPs) were determined to explore the NLO assets of chromophores. The NBO analysis elucidated that the intramolecular interactions, electron delocalization and hyper conjugative interactions played a significant role in stabilizing the compounds. The NPA and MEP analyses were performed for predicting the charge distributions for the atoms and chemical reactivity regions of studied compounds. The GRPs were calculated utilizing FMOs energies and compound 1 was found as soft, less stable, more reactive molecule from other compounds The non-linear optical (NLO) findings exploited that 1–5 compounds showed 40.6, 34.2, 34.6, 35.4 and 29.1 times greater hyperpolarizability than the urea and can be utilized as efficient optoelectronic materials. [ABSTRACT FROM AUTHOR]

The synthesis of 1-benzyl-2-((2-Aminoethyl) amino)-5-oxopyrrolidine-3,4-diyl diacetate (boad), an oxopyrrolidine type ligand; designed to coordinate lanthanides (Eu3+ and Tb3+) to get luminescent material. The target complexes showed good photoluminescence properties, which indicate that this type of compound can be used as sensitizers having luminescence for the green (Tb3+) and red (Eu3+) emission. The obtained results revealed that sensitizer efficiency can be improved by adding ligands like acac (Eu(acac)3, which has also enhanced the luminescence quantum output and period for Eu3+ ions. The ground state geometries were developed by using density functional theory at B3LYP/6-31G** level. The charge transfer analysis and electronic properties were performed. The Europium and Terbium complexes formation with boad ligand was explored based on molecular electrostatic potential, MDC-q charges, and frontier molecular orbitals (FMOs) analysis. [ABSTRACT FROM AUTHOR]

This study reports the synthesis of sulfonamide‐derived Schiff bases as ligands L1 and L2 as well as their transition metal complexes [VO(IV), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)]. The Schiff bases (4‐{E‐[(2‐hydroxy‐3‐methoxyphenyl)methylidene]amino}benzene‐1‐sulfonamide (L1) and 4‐{[(2‐hydroxy‐3‐methoxyphenyl)methylidene]amino}‐N‐(5‐methyl‐1,2‐oxazol‐3‐yl)benzene‐1‐sulfonamide (L2) were synthesized by the condensation reaction of 4‐aminobenzene‐1‐sulfonamide and 4‐amino‐N‐(3‐methyl‐2,3‐dihydro‐1,2‐oxazol‐5‐yl)benzene‐1‐sulfonamide with 2‐hydroxy‐3‐methoxybenzaldehyde in an equimolar ratio. Sulfonamide core ligands behaved as bidentate ligands and coordinated with transition metals via nitrogen of azomethine and the oxygen of the hydroxyl group. Ligand L1 was recovered in its crystalline form and was analyzed by single‐crystal X‐ray diffraction technique which held monoclinic crystal system with space group (P21/c). The structures of the ligands L1and L2 and their transition metal complexes were established by their physical (melting point, color, yields, solubility, magnetic susceptibility, and conductance measurements), spectral (UV–visible [UV–Vis], Fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and mass analysis), and analytical (CHN analysis) techniques. Furthermore, computational analysis (vibrational bands, frontier molecular orbitals (FMOs), and natural bonding orbitals [NBOs]) were performed for ligands through density functional theory utilizing B3LYP/6‐311+G(d,p) level and UV–Vis analysis was carried out by time‐dependent density functional theory. Theoretical spectroscopic data were in line with the experimental spectroscopic data. NBO analysis confirmed the extraordinary stability of the ligands in their conjugative interactions. Global reactivity parameters computed from the FMO energies indicated the ligands were bioactive by nature. These procedures ensured the charge transfer phenomenon for the ligands and reasonable relevance was established with experimental results. The synthesized compounds were screened for antimicrobial activities against bacterial (Streptococcus aureus, Bacillus subtilis, Eshcheria coli, and Klebsiella pneomoniae) species and fungal (Aspergillus niger and Aspergillus flavous) strains. A further assay was designed for screening of their antioxidant activities (2,2‐diphenyl‐1‐picrylhydrazine radical scavenging activity, total phenolic contents, and total iron reducing power) and enzyme inhibition properties (amylase, protease, acetylcholinesterase, and butyrylcholinesterase). The substantial results of these activities proved the ligands and their transition metal complexes to be bioactive in their nature. [ABSTRACT FROM AUTHOR]

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10−17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics. [ABSTRACT FROM AUTHOR]

• Designing of eight new acceptors (MS1-MS8) for OSCs. • Investigation of electronic and photophysical properties. • Better λ max , TDM, E g , PDOS, MEP, and E b than R. • A better choice for high-performance solar cells. Herein, we report the end-capped modification of the recently reported acceptor CH1007. Considering the importance of non-fullerene acceptors, we theoretically designed a series of benzo-thiadiazole core-based acceptors (MS1-MS8) to enhance the photophysical, and photovoltaic properties of the acceptors. In this study, properties like frontier molecular orbitals, maximum absorption, transition density matrix, open-circuit voltage, binding and excitation energies, dipole moment, and partial density of states were estimated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) using B3LYP functional with bases set 6-31G(d,p). When studied computationally, all engineered compounds exhibited red-shift in the absorption spectrum and λ max lie in the range of 734–900 nm, compared to the reference compound (λ max = 735 nm). The designed acceptors exhibited low reorganizational energies (better charge transfer property), low binding and excitation energies besides narrow HOMO-LUMO bandgap. Moreover, the donor–acceptor complexes of the designed acceptors MS1 and MS4 have been studied with well-known standard donors PTB7-Th & PM6. The distribution of electron density in the resultant donor–acceptor complexes showed successful shift of electron density from donor moiety to acceptor moiety. The results revealed that such type of end-capped modifications in acceptors can lead to better photophysical and optoelectronic properties. So, designed compounds have potential to enhance the capacity of acceptor molecules and are therefore, suggested for the development of more efficient organic solar cells (OSCs). [ABSTRACT FROM AUTHOR]

Context: In this study, new visible light harvesting dyes (MBR1–MBR5) have been designed as efficient materials with silyl based anchoring abilities on semiconducting units for future dye-solar cells applications. Their unique molecular structures of novel D-π-ASemiconductor type were evaluated thoroughly by density functional theory (DFT) calculations. To enhance the optical performance in visible region, a novel dye structure (MBR) was derived from the chemical structure of mordant black (MB) dye with electron acceptor semiconducting units (MBR1–MBR5). Methods: The Coulomb-attenuating Becke, 3-parameter, Lee–Yang–Parr (CAM-B3LYP) functional, which had a hybrid and long-range correlation with 6-31G + (d,p), generated a λ max (683 nm) that was very comparable to its experimental value (672 nm). The energies of highest occupied molecular orbitals (HOMO), lowest unoccupied molecular orbitals (LUMO), and their HOMO–LUMO energy gaps (HLG) were calculated. Their ionization potentials (IP) varied from 5.616 to 8.320 eV, demonstrating their good electron donating trend. The λ max values of dyes displayed a significant red shift from MBR (682 nm) value with range 565–807 nm except MBR1 which was slightly blue shifted. The dye MBR4, which had the smallest HLG (0.23 eV) had the greatest second order nonlinear optical (NLO) response of 144,234 Debye-Angstrom−1. The DFT calculated results provided insight into the creation of new silyl anchoring groups for future DSSCs material designs with increased stability and effectiveness. The goal of the current study is to forecast the development of novel NLO materials with a D-π-ASemiconductor design that use semiconductors as anchoring groups to adhere to a surface. [ABSTRACT FROM AUTHOR]

A series of derivatives (DOCD2–DOCD6) with D–π–A configuration was designed by substituting various efficient donor moieties via the structural tailoring of o-DOC6-2F. Quantum-chemical approaches were used to analyze the optoelectronic properties of the designed chromophores. Particularly, M06/6-311G(d,p) functional was employed to investigate the non-linear optical (NLO) response (linear polarizability ⟨α⟩, first (βtot) and second (γ tot) order hyperpolarizabilities) of the designed derivatives. A variety of analyses such as frontier molecular orbital (FMO), absorption spectra, transition density matrix (TDMs), density of states (DOS), natural bond orbital (NBO) and global reactivity parameters (GRPs) were employed to explore the optoelectronic response of aforementioned chromophores. FMO investigation revealed that DOCD2 showed the least energy gap (1.657 eV) among all the compounds with an excellent transference of charge towards the acceptor from the donor. Further, DOS pictographs and TDMs heat maps also supported FMO results, corroborating the presence of charge separation states along with efficient charge transitions. NBO analysis showed that π-linker and donors possessed positive charges while acceptors retained negative charges confirming the D–π–A architecture of the studied compounds. The λmax values of designed chromophores (659.070–717.875 nm) were found to have broader spectra. The GRPs were also examined utilizing energy band gaps of EHOMO and ELUMO for the entitled compounds. Among all the derivatives, DOCD2 showed the highest values of βtot (7.184 × 10–27 esu) and γ tot (1.676 × 10–31 esu), in coherence with the reduced band gap (1.657 eV), indicating future potentiality for NLO materials. [ABSTRACT FROM AUTHOR]

The development of an effective building blocks considered the boon in constructing highly efficient nonfullerene electron acceptors (NFEAs). The first theoretical design and investigation of environmental-friendly groups for changing potential end-capped electron acceptor molecules for high-performance environmental-friendly OSCs is proposed in this study. We developed BTT-based A – π – D – π – A (acceptor–bridge–core–bridge–acceptor) type, neoteric Bat-shaped environmental-friendly acceptor molecules (K1–K6) for the first time by replacing the electronegative –F group of BTT with four electron-withdrawing (–CN, –COOCH3, –NO2, –Cl) groups. K1–K6 has its exciton-binding energy ( E b ), open-circuit voltage ( V oc ), frontier molecular orbital analysis (FMO), transition density matrix (TDM) analysis, electron and hole reorganization energy (λ e, λ h), density of state (DOS) graphs, and transition energy Ex values computed and compared to the recently proposed high-performance BTT molecule. According to the research, the photovoltaic, photo-physical and electrical applications of proposed molecules K1–K6 are comparable to those of R. When compared to reference R and proposed molecules, K6 tested to be the proverbial optoelectronic compound for OSCs due to its low E g (2.05 eV), lowest E x (1.57 eV), highest λ max values of 790.61 nm in CHCl3, 0.95 V value for V oc and comparable E b (0.482 eV). The superposition of orbitals and lucrative charge shift from the highest occupied molecular orbital (HOMO) (PTB7-Th) to the lowest unoccupied molecular orbital (LUMO) were verified by charge transfer study among the K6: PTB7-Th combine. As a result, the proposed molecules (K1–K6) with exceptional optoelectronic capabilities are suggested as the best harmless alternative materials for creating proficient and environmental-friendly OSCs. Benzotrithiophene-based bat-shaped non-fullerene acceptor materials (K1-K6) have been designed to enhance the photophysical and optoelectronics properties. These materials (K1-K6) along with reference (R) have been visualized theoretically. The photovoltaic and optoelectronic properties have been estimated with density functional theory (DFT) and time-dependent (TD-DFT) calculations, and this strategy is a criterion to design required photovoltaic materials for efficient OSCs. [ABSTRACT FROM AUTHOR]

In current era, non-fullerene (NF) chromophores have been reported as significant NLO materials due to promising optoelectronic properties. Therefore, a series of NF based chromophores abbreviated as TPBD2-TPBD6 with D–π–A architecture was designed from the reference compound (TPBR1) by its structural tailoring with an efficient donor and various acceptor groups for the first time. First, the structures of said compounds were optimized at M06-2X/6-311G (d,p) level. Further, the optimized structures were utilized to execute frontier molecular orbitals (FMOs), UV–Visible (UV–Vis) absorption, density of states (DOS) and transition density matrix (TDM) analyses at the same level to understand the non-linear (NLO) response of TPBR1 and TPBD2-TPBD6. Promising NLO results were achieved for all derivatives i.e., the highest amplitude of linear polarizability ⟨α⟩, first (βtotal) and second (γ total) hyperpolarizabilities than their parent molecule. The compound TPBD3 was noted with the most significant NLO properties as compared to the standard molecule. The structural modeling approach by utilizing the acceptor molecules has played a prominent role in attaining favorable NLO responses in the molecules. Thus, our study has tempted the experimentalists to synthesize the proposed NLO materials for the modern optoelectronic high-tech applications. [ABSTRACT FROM AUTHOR]

Now a days, researchers are constantly doing efforts to upgrade the performance of solar based devices with the aim of increasing the role of photovoltaic materials in modern hi-tech optoelectronic applications. Realizing the recent energy conditions across the globe, research is diverted from fullerene to non-fullerene electron acceptor moieties in this era, considering their remarkable contribution in organic solar cells (OSCs). Therefore, we designed seven novel non-fullerene fused ring electron acceptor chromophores (MD2–MD8) from DOC2C6-2F by structural tailoring with different acceptors at end-capped units. DFT study was performed at B3LYP functional to discover the opto-electronic characteristics of the newly tailored chromophores. Various analysis such as frontier molecular orbitals (FMOs), transition density matrix (TDM), density of states (DOS), binding energy (Eb), reorganization energy, open circuit voltage (Voc) was carried out to comprehend the photovoltaic response of MD2–MD8. Decrease in band gaps (1.940–1.571 eV) with wider absorption spectrum (725.690–939.844 nm in chloroform) along with greater charge transfer rate from HOMO towards LUMO were examined in derivatives as compared to MR1 (Egap = 1.976 eV, λmax = 738.221 nm) except MD7. Further, in all derivatives, smaller values of Eb (0.252–0.279 eV) were examined than that of reference (0.296 eV). These lower binding energy values of MD2–MD8 indicated the higher rate of excitation dissociation with lager charger transfer rate than MR1, which further supported by DOS and TDM analyses. Additionally, least reorganization energy in the aforesaid compounds for hole with electron was also inspected. Moreover, Voc a good photovoltaic response was noted for all studied compounds which indicated that these compounds are suitable to synthesize OSCs in future. [ABSTRACT FROM AUTHOR]

In this study, five new asymmetrical fullerene-free acceptor molecules (N1 to N5) have been designed for organic solar cell applications. Density functional theory and time dependent density functional theory has been employed for exploring the opto-electronic, photovoltaic and geometric properties of the designed molecules. A narrow energy band gap with high red-shifting in the absorption spectrum has been noted. High open circuit voltage with good values of reorganizational energy of electron suggested that designed molecules are effective contributor for solar cell applications. Transition density matrix and frontier molecular orbitals analysis also expressed the presence of charge density within a molecule with different types of transitions. Finally, blend study also performed for exploring the charge transfer between donor polymer and acceptor molecule. [ABSTRACT FROM AUTHOR]

The (S)‐4‐bromo‐N‐(1‐phenylethyl)benzamide (3) was synthesized in excellent yield (93 %) by the reaction of 4‐bromobenzoic acid (1) and (S)‐1‐phenylethanamine (2) with the coupling reagent titanium tetrachloride (TiCl4). Further, the Pd(0) catalyst was employed to form (S)‐4‐bromo‐N‐(1‐phenylethyl)benzamide analogues (5 a‐i) by reacting various aryl boronic acids with 4‐bromo‐N‐(1‐phenylethyl)benzamide (3) in moderate to good yields (62‐89 %). Furthermore, DFT studies were carried out to compute optimized geometries, frontier molecular orbitals, polarizability (α), hyperpolarizability (β), MESP, reactivity descriptors, and NMR spectra. The measured NMR values matched the experimental NMR values well. In this series (5 a‐i), we predicted that the highest energy difference between the HOMO‐LUMO of compound (5 a) has 4.98 eV, resulting in a more stable compound, and compound (5 g) has the lowest energy difference between the HOMO‐LUMO 4.63 eV, resulting in the least stable compound. Compound (5h) has the highest hyperpolarizability (β) value, exhibits a better non‐linear optical (NLO) behaviour compared as compare to other synthesized compounds in the series. [ABSTRACT FROM AUTHOR]

In organic photovoltaic technology, tailoring the acceptor or donor unit to enhance intramolecular charge transfer is a well-known approach, however, the effect of modifying conjugated bridge units is an underdeveloped phenomenon. In this study, this approach has been focused, where a series of conjugated bridges including, a) electron-excessive heterocycles, b) electron-deficient heterocycles, and c) short-chain unsaturated hydrocarbons have been substituted from thiophene bridge-containing D-π-A; N-methyl-4,5-diazacarbazole (donor) and bay-annulated indigo (acceptor) molecule. This quantum chemical study aims to investigate the effect of various types of π-conjugated bridges on the electronic structure and solar cell activity of already reported material. The selected π-conjugated bridges include electron-excessive (furan, pyrrole, & thiophene) and electro-deficient (diazine, tetrazine, & pyridine) heterocycles, and short-chain hydrocarbons (ethylene & ethyne). The optimized structural parameters e.g., dihedral angles (θ), distortion energies (E dis), & bond distances (d), and electronic behaviour i.e., Frontier Molecular Orbitals (FMO), Electrostatic Potentials (ESP), Density of States (DOS) spectra, dipole moments (μ), and absorption spectra of the hypothetically designed molecules are estimated using density functional theory calculations. The solar cell proficiency is investigated with transition dipole moment (μ T), reorganization energy (RE), Transition density matrix (TDM), exciton binding energy (E b), and open circuit voltage (Voc). Our finding encompassed that our designed D-π-A molecules show significant improvement in their electronic behaviour, especially when the thiophene bridge of the reference molecule is substituted with the excess electron heterocycles, especially pyrrole. The HOMO-LUMO gap of this particular molecule (MPy) is reduced to 2.07 eV, resulting in the significant charge transfer between donor and acceptor units (0.15 e-). Moreover, the results of RE, TDM, E b , and V oc also support the high solar cell efficiency of pyrrole-containing molecules. [Display omitted] • Photovoltaic properties enhancement through variation of conjugated bridge between donor- π-acceptor groups. • B3LYP-(BJ)D3/6–31+G(d, p) level of DFT was adopted. • The significant reduction of HOMO-LUMO gap (up to 2.07 eV) was observed. • RE, TDM, E b , and V oc analyses supported the high solar cell efficiency. [ABSTRACT FROM AUTHOR]

Designing of anode nanomaterials with an optimum cell voltage is an important challenge for high-performance lithium (Li) ion batteries. In this study, we have investigated the electrochemical potential of pristine and Li-doped magnesium oxide (Mg 12 O 12) and zinc oxide (Zn 12 O 12) fullerenes through density functional theory (DFT) simulations, with a focus on their potential applications in lithium-ion batteries. Specifically, we investigated the halide ion encapsulated oxide nanocages as a means to achieve this improvement. We examined both unaltered and halide encapsulated Mg 12 O 12 and Zn 12 O 12 with Li atom/lithium cation (Li/Li+). Our investigation delves into the geometric and electrochemical characteristics of Li/Li+ interactions with Mg 12 O 12 and Zn 12 O 12 nanocages. We analyzed adsorption energies (E ad) and frontier molecular orbitals (FMOs) of Li/Li+ ions with these nanocages to gain insights into how neutral or ionic Li affects their geometric and electrochemical properties. The initial cell voltages of bare Mg 12 O 12 and Zn 12 O 12 are found to be 0.61 and 0.57 V, primarily due to marginal distinctions in the adsorption energies of Li and Li+ bound systems. Notably, the encapsulation of various halides into Mg 12 O 12 and Zn 12 O 12 nanocages significantly enhanced the cell voltage. Among the considered halides, the encapsulation of fluoride anion (F −) into Mg 12 O 12 and Zn 12 O 12 stands out, leading to a remarkable increase in cell voltage of 4.05 and 3.55 V for lithium-ion batteries, respectively. Moreover, the use of toluene solvent further increased the E ad values of Li cation with pure and halides encapsulated oxides (Mg 12 O 12 and Zn 12 O 12) nanocages. Ultimately, the Gibb's free also decreased along with the decrease in the cell voltage which is encountered in the acceptable range. The most suitable anode nanomaterial is suggested to be Li doped F−@Mg 12 O 12 which has the most acceptable cell voltage of 1.59 V. The work also leads to more research work on the designing of halides encapsulated oxides fullerenes based secondary batteries for use in electrochemical energy storage devices. This work is a full-length guideline for the experimentalist to synthesize such systems to overcome the energy crises. [Display omitted] • Theoretically models of magnesium and zinc oxides nanocages are analyzed for use as anode in Na-ion batteries. • The electrochemical performance is enhanced by encapsulating halides inside magnesium and zinc oxides nanocages. • The energy gaps of both oxides nanocages are decreased by halides encapsulation and making them conductors. • The highest cell voltages of L i / F − @Mg 12 O 12 and L i / F − @Zn 12 O 12 are 4.05 and 3.55 V, respectively. [ABSTRACT FROM AUTHOR]

Herein, antibacterial transition metal complexes of ML2 type having o‐sulfamoylbenzoic acid as ligand were synthesized from saccharin. All characterization techniques confirmed the syntheses of non‐ionic transition metal MnII (3), CoII (4), NiII (5), CuII (6), and ZnII (7) complexes, where mono‐anionic o‐sulfamoylbenzoic acid acts as a weak field ligand. The FT‐IR, elemental analysis, and magnetic susceptibility studies suggested octahedral and square pyramidal geometries depending on the nature of metal ions. Biological activity of these complexes was studied by using six bacterial strains. Interestingly, the bacterial strains Escherichia coli and Klebsiella aerogenes were inhibited to the maximum level by 6. Among aforementioned five complexes, 4 and 6 were found in crystalline form. Apart from experimental study, DFT study was also performed for entitled complexes at the M06/6‐311G(d,p) level. A comparative investigation was performed for geometrical parameters and vibrational analysis, and an agreement was obtained. Natural bonding orbital investigations expressed larger value of stabilization energy 21 kcal/mol for 3, 4, and 6 while 42 kcal/mol for 5 and 7. Furthermore, global reactivity findings also disclosed higher value of hardness (2.44–3.09 eV) for entitled chromophores, hence, showed more stability. Moreover, frontier molecular orbital (FMO) findings revealed a larger band gap (4.48–6.19 eV) with higher values of LUMO found for all complexes. [ABSTRACT FROM AUTHOR]

Development of novel materials for organic solar cells is a booming area of current research. Fused-ring electron accepters are the potential agents of revolution in organic photovoltaic devices and revealing high efficiency in organic solar cells. This study highlights the novel quad-rotor-shaped molecules as first example of efficient fused-ring non-fullerene acceptor materials with proficient photovoltaic parameters for their utilization in high-performance organic solar cells. First time, eight quad-rotor-shaped fused-ring electron accepters (QRFR-1–QRFR-8) are developed via modulating end-caps of experimentally synthesized (BFTT-TN) molecule (QRFR). Optoelectronic properties of proposed molecules are determined using frontier molecular orbitals (FMO), UV–Visible, density of state (DOS), overlap DOS (ODOS), transition density matrix (TDM) heat maps, open circuit voltage (Voc), binding energies (Eb), reorganization energy of electron (λe), hole (λh), charge transfer analysis, and compared with reference QRFR. All proposed fused-ring electron accepters disclose less energy gap and λmax in near IR region than QRFR after end-capped engineering. Highest Voc with respect to HOMOPM6–LUMOacceptor is found 1.66 V in QRFR-6 than QRFR (1.63 V). Eb values of QRFR-1–QRFR-8 are found better and comparable with QRFR. The λe is found smaller than QRFR in all molecules except QRFR-5. The proposed quad-rotor-shaped molecules exhibit proficient photovoltaic features and can serve as best candidate for organic solar cells when blended with PM6 film. This study not only enlightens the researchers to use end-capped reforms as effective tactic for designing materials, but also provides novel quad-rotor-shaped materials to experimentalist for synthesis and their usage in future application of organic solar cells. [ABSTRACT FROM AUTHOR]

Non-fullerene based organic compounds are considered promising materials for the fabrication of modern photovoltaic materials. Non-fullerene-based organic solar cells comprise of good photochemical and thermal stability along with longer device lifetimes as compared to fullerene-based compounds. Five new non-fullerene donor molecules were designed keeping in view the excellent donor properties of 3-bis(4-(2-ethylhexyl)-thiophen-2-yl)-5,7-bis(2ethylhexyl) benzo[1,2-:4,5-c′]-dithiophene-4,8-dione thiophene-alkoxy benzene-thiophene indenedione (BDD-IN) by end-capped modifications. Photovoltaic and electronic characteristics of studied molecules were determined by employing density functional theory (DFT) and time dependent density functional theory (TD-DFT). Subsequently, obtained results were compared with the reference molecule BDD-IN. The designed molecules presented lower energy difference (ΔΕ) in the range of 2.17–2.39 eV in comparison to BDD-IN (= 2.72 eV). Moreover, insight from the frontier molecular orbital (FMO) analysis disclosed that central acceptors are responsible for the charge transformation. The designed molecules were found with higher λmax values and lower transition energies than BDD-IN molecule due to stronger end-capped acceptors. Open circuit voltage (Voc) was observed in the higher range (1.54–1.78 V) in accordance with HOMOdonor–LUMOPC61BM by designed compounds when compared with BDD-IN (1.28 V). Similarly, lower reorganization energy values were exhibited by the designed compounds in the range of λe(0.00285–0.00370 Eh) and λh(0.00847–0.00802 Eh) than BDD-IN [λe(0.00700 Eh) and λh(0.00889 Eh)]. These measurements show that the designed compounds are promising candidates for incorporation into solar cell devices, which would benefit from better hole and electron mobility. [ABSTRACT FROM AUTHOR]

The global need for renewable sources of energy has compelled researchers to explore new sources and improve the efficiency of the existing technologies. Solar energy is considered to be one of the best options to resolve climate and energy crises because of its long-term stability and pollution free energy production. Herein, we have synthesized a small acceptor compound (TPDR) and have utilized for rational designing of non-fullerene chromophores (TPD1–TPD6) using end-capped manipulation in A2–A1–D–A1–A2 configuration. The quantum chemical study (DFT/TD-DFT) was used to characterize the effect of end group redistribution through frontier molecular orbital (FMO), optical absorption, reorganization energy, open circuit voltage (Voc), photovoltaic properties and intermolecular charge transfer for the designed compounds. FMO data exhibited that TPD5 had the least ΔE (1.71 eV) with highest maximum absorption (λmax) among all compounds due to the four cyano groups as the end-capped acceptor moieties. The reorganization energies of TPD1–TPD6 hinted at credible electron transportation due to the lower values of λe than λh. Furthermore, open circuit voltage (Voc) values showed similar amplitude for all compounds including parent chromophore, except TPD4 and TPD5 compounds. These designed compounds with unique end group acceptors have the potential to be used as novel fabrication materials for energy devices. [ABSTRACT FROM AUTHOR]

Organic compounds expressed excellent nonlinear optical (NLO) performance which can effectively be utilized in numerous fields like optical fibers, optical communications, and optical modulation. In this study, eight new compounds abbreviated as HCPBD1–HCPBD8 were designed by structural alterations at donor and acceptor parts using HCPBR (hexyl-2-cyano-3-[4-(pyren-1-yl) benzen-1-yl]) as reference molecule for promising nonlinear optical responses. For this purpose, natural bonding orbital (NBO), absorption spectra, frontier molecular orbitals (FMOs) and nonlinear optical (NLO) computations of HCPBR and HCPBD1–HCPBD8 were employed via M06 level of theory using 6-31G(d,p) basis set in dichloromethane solvent. All the designed molecules (HCPBD1–HCPBD8) showed smaller HOMO–LUMO energy band gap in comparison to HCPBR. Furthermore, these derivatives expressed larger softness magnitudes than HCPBR which indicated derivatives were more polarizable than parent molecule. Additionally, HCPBD1–HCPBD8 displayed red shift than HCPBR, particularly, HCPBD8 exhibited highest λmax as 1003.75 nm followed by low transition energy. Accompanying with, NBO computations revealed that prolonged hyper-conjugation and strong internal molecular interaction play key role in their stabilization as well as support to their NLO responses. Consequently, linear polarizability 〈α〉 and NLO responses such as first hyperpolarizability (β) and second-order hyperpolarizability 〈γ〉 values of HCPBD1–HCPBD8 were higher than HCPBR. Interestingly, HCPBD8 contained highest values 1576.05 (a.u.), 293,462.15 (a.u.) and 91.57 × 106 (a.u.) of 〈α〉, βtotal and 〈γ〉, respectively. This study showed that structural tailoring with various donor and acceptor units plays a crucial role to obtain alluring NLO material for optoelectronic applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • DFT study of electron rich complexes (Ca-1-TM) as potential NLO material. • Demonstration of charge distribution on metals in designed complexes by NBO analysis. • Modification in electronic properties of complexes using NBO and FMO analysis. • Evaluation of controlling factors of first hyperpolarizabilities by two level method. • Higher NLO response of Ca-1-Co complex among studied complexes. Herein, the Janus type complexes have been designed that have the fame as potential candidates in nonlinear optical (NLO 1 1 NLO (Nonlinear optics).) materials due to excess electrons. In present work, novel class of excess electronic compounds termed as transition metalides AE-1-TM 2 2 AE (Alkaline Earth), 1 (complexant = C 6 H 9 F 3), TM (Transition Metal). complexes (AE = Ca, Fe/Co/Ni/Cu/Zn) 3 3 Ca (Calcium), Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Zn (Zinc). have been designed theoretically using highly polarized all axially cis -1,3,5-trifuorocyclohexane 1 (C 6 H 9 F 3) as complexant bearing a larger dipole moment of 5.42 D. The electronic, thermodynamic and geometric features of Ca-1-TM were studied using M06-2x|6-31++G(d,p) level of theory. More distinctively, transition metalide nature of the complexes has been verified by NBO 4 4 NBO (Natural Bond Orbitals). (Natural Bond Orbital) and HOMOs 5 5 HOMOs (Highest occupied molecular orbitals). (Highest Occupied Molecular Orbital) density distribution analysis. The thermodynamic stability of transition metalides is evident from large values of interaction energies (-6.99 to −25.01 kcal/mol). The designed complexes showed low excitation energies (2.09–4.01 eV) and high first hyperpolarizabilities (β o) up to 2.16 × 105 (au). Moreover, hyper rayleigh scattering (β HRS) was computed for evaluation of NLO response of complexes. Dipolar and octupolar nature of Ca- 1 -TM complexes have also been confirmed by the depolarization ratio (DR 6 6 DR (Depolarization Ratio).). The higher values of hyperpolarizabilities provided evidences for the existence of excess electrons around transition metals. Two-level model approach was used for rationalization of hyperpolarizabilities. The results illustrated that the generation of these complexes is a novel entry in the metalide that can be recognized as preferable way for designing NLO materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • TQBQ-COF for detecting Industrial pollutants including NH 3 , H 2 S, HCN and PH 3. • Demonstration of nature of interactions by NCI and QTAIM analysis. • Variation in electronic properties of complexes justified by NBO, EDD and FMO analysis. • High sensitivity of TQBQ-COF for H 2 S compared to other analytes. The physisorption of pollutant gases (NH 3, HCN, H 2 S and PH 3) on TQBQ-COF has been explored using DFT calculations. The strength and nature of interactions were determined through interaction energy, non-Covalent interactions- Reduced Density Gradient (NCI-RDG) plots, Frontier Molecular Orbital (FMO), Natural bond orbital (NBO), Electron Density Difference (EDD) and Quantum Theory of Atoms In Molecule (QTAIM) analysis. The optimized geometries and interaction energy calculations revealed that the analytes interacted with Oxygen and Nitrogen atoms of TQBQ-COF leading to adsorption energy ranging from −10.66 to −5.85 kcal/mol. The values of recovery time were in agreement to that of interaction energy and decreased with the increase in temperature. The NCI-RDG plots and QTAIM analysis revealed the presence of weak van der Waals forces in all complexes and partial covalent character in H 2 S@TQBQ-COF. Charge transfer study (employing NBO and EDD analysis) depicted the transfer of charge from surface to analytes. The study of HOMO-LUMO energy gap in FMO analysis depicted the high sensitivity of TQBQ-COF for H 2 S and NH 3 compared to HCN and PH 3 due to significant lowering of HOMO-LUMO energy gap upon the adsorption of H 2 S and NH 3 on TQBQ-COF. [ABSTRACT FROM AUTHOR]

[Display omitted] • DFT study of electron rich complexes (Ca-1-TM) as potential NLO material. • Demonstration of charge distribution on metals in designed complexes by NBO analysis. • Modification in electronic properties of complexes using NBO and FMO analysis. • Evaluation of controlling factors of first hyperpolarizabilities by two level method. • Higher NLO response of Ca-1-Co complex among studied complexes. Herein, the Janus type complexes have been designed that have the fame as potential candidates in nonlinear optical (NLO 1 1 NLO (Nonlinear optics).) materials due to excess electrons. In present work, novel class of excess electronic compounds termed as transition metalides AE-1-TM 2 2 AE (Alkaline Earth), 1 (complexant = C 6 H 9 F 3), TM (Transition Metal). complexes (AE = Ca, Fe/Co/Ni/Cu/Zn) 3 3 Ca (Calcium), Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Zn (Zinc). have been designed theoretically using highly polarized all axially cis -1,3,5-trifuorocyclohexane 1 (C 6 H 9 F 3) as complexant bearing a larger dipole moment of 5.42 D. The electronic, thermodynamic and geometric features of Ca-1-TM were studied using M06-2x|6-31++G(d,p) level of theory. More distinctively, transition metalide nature of the complexes has been verified by NBO 4 4 NBO (Natural Bond Orbitals). (Natural Bond Orbital) and HOMOs 5 5 HOMOs (Highest occupied molecular orbitals). (Highest Occupied Molecular Orbital) density distribution analysis. The thermodynamic stability of transition metalides is evident from large values of interaction energies (-6.99 to −25.01 kcal/mol). The designed complexes showed low excitation energies (2.09–4.01 eV) and high first hyperpolarizabilities (β o) up to 2.16 × 105 (au). Moreover, hyper rayleigh scattering (β HRS) was computed for evaluation of NLO response of complexes. Dipolar and octupolar nature of Ca- 1 -TM complexes have also been confirmed by the depolarization ratio (DR 6 6 DR (Depolarization Ratio).). The higher values of hyperpolarizabilities provided evidences for the existence of excess electrons around transition metals. Two-level model approach was used for rationalization of hyperpolarizabilities. The results illustrated that the generation of these complexes is a novel entry in the metalide that can be recognized as preferable way for designing NLO materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • TQBQ-COF for detecting Industrial pollutants including NH 3 , H 2 S, HCN and PH 3. • Demonstration of nature of interactions by NCI and QTAIM analysis. • Variation in electronic properties of complexes justified by NBO, EDD and FMO analysis. • High sensitivity of TQBQ-COF for H 2 S compared to other analytes. The physisorption of pollutant gases (NH 3, HCN, H 2 S and PH 3) on TQBQ-COF has been explored using DFT calculations. The strength and nature of interactions were determined through interaction energy, non-Covalent interactions- Reduced Density Gradient (NCI-RDG) plots, Frontier Molecular Orbital (FMO), Natural bond orbital (NBO), Electron Density Difference (EDD) and Quantum Theory of Atoms In Molecule (QTAIM) analysis. The optimized geometries and interaction energy calculations revealed that the analytes interacted with Oxygen and Nitrogen atoms of TQBQ-COF leading to adsorption energy ranging from −10.66 to −5.85 kcal/mol. The values of recovery time were in agreement to that of interaction energy and decreased with the increase in temperature. The NCI-RDG plots and QTAIM analysis revealed the presence of weak van der Waals forces in all complexes and partial covalent character in H 2 S@TQBQ-COF. Charge transfer study (employing NBO and EDD analysis) depicted the transfer of charge from surface to analytes. The study of HOMO-LUMO energy gap in FMO analysis depicted the high sensitivity of TQBQ-COF for H 2 S and NH 3 compared to HCN and PH 3 due to significant lowering of HOMO-LUMO energy gap upon the adsorption of H 2 S and NH 3 on TQBQ-COF. [ABSTRACT FROM AUTHOR]

[Display omitted] • Triazine based sensor displayed excellent selectivity for sequential detection of Hg2+ and L-Cysteine. • Sensor was deployed for the detection of Hg2+ and Cys in real samples (industrial water, whitening creams and milk). • Detection of Hg2+ was based on chelation enhanced fluorescence (CHEF) and inhibition of ICT. • Extensive DFT calculations supported the plausible sensing mechanisms and nature of interactions. Triazine based fluorescent sensor TBT was rationally designed and synthesized to achieve sequential detection of Hg2+ and L-cysteine based on the presence of sulfur moiety and suitable cavity in the molecule. Sensor TBT exhibited excellent sensing potential for the selective detection of Hg2+ ions and L-cysteine (Cys) in real samples. Upon addition of Hg2+ to sensor TBT , enhancement in emission intensity of sensor TBT was observed which was accredited to the presence of sulfur moiety and size of cavity in the sensor. Upon interaction with Hg2+ blockage of intramolecular charge transfer (ICT) along with chelation-enhanced fluorescence (CHEF) resulted in the increase in fluorescence emission intensity of sensor TBT. Further, TBT -Hg2+ complex was employed for the selective detection of Cys through fluorescence quenching mechanism. This was attributed to the significantly stronger interaction of Cys with Hg2+, which resulted in the formation of Cys-Hg2+ complex and subsequently sensor TBT was released from TBT -Hg2+ complex. The nature of interaction between TBT -Hg2+ and Cys-Hg2+ complex was evaluated through 1H NMR titration experimentations. Extensive DFT studies were also carried out which include thermodynamic stability, frontier molecular orbitals (FMO), density of states (DOS), non-covalent interaction (NCI), quantum theory of atom in molecule (QTAIM), electron density differences (EDD) and natural bond orbital (NBO) analyses. All the studies supported the non-covalent type of interaction between analytes and sensor TBT. The limit of detection for Hg2+ ions was found to be as low as 61.9 nM. Sensor TBT was also employed for the quantitative detection of Hg2+ and Cys in real samples. Additionally, logic gate was fabricated by using sequential detection strategy. [ABSTRACT FROM AUTHOR]

A series of new organic dyes (T1 - T6) with nonfullerene acceptors have been theoretically designed around the chemical structure of tyrian purple (T) natural dye. For their ground state energy parameters, all the molecular geometries of those dyes were optimized by density functional theory (DFT) at its Becke, 3-parameter, Lee–Yang–Parr (B3LYP) level of theory with 6–31G+(d,p) basis sets. When benchmarking against several long range and range separated levels of theory, the Coulomb attenuated B3LYP (CAM-B3LYP) produced most accurate absorption maxima (λ max) value to that of T so it was further employed for further Time dependent DFT (TD-DFT) calculations. Frontier molecular orbitals (FMOs) with natural bond orbital (NBO) studies were used to study their intra molecular charge transfer (ICT). All of the dyes had their energy gaps (E g) values between their FMOs to range around 0.96–3.39 eV, whereas the starting reference dye had an E g of 1.30 eV. Their ionization potential (IP) values were ranged to be 3.07–7.25 eV which indicated their nature to loss electrons. The λ max in chloroform was marginally red-shifted with a value 600–625 from T (580 nm). The dye T6 showed its highest linear polarizability (< α >), and first and second order hyperpolarizabilities (β and γ). The synthetic experts can find the present research to design finest NLO materials for current and future uses. [Display omitted] • A study to highlight the importance of theoretical modeling to improve DSSCs performance. • Efficient utilization of Tyrian purple natural dye as a donor moiety. • Exploration of nonlinear optical (NLO) performance for new dyes. • The results shed insights into the design and optimization of organic DSSCS. [ABSTRACT FROM AUTHOR]

[Display omitted] • Superalkalis doped bowel shaped silicon carbide complexes are studied via DFT method. • All complexes have electronic and thermodynamic stability. • First hyperpolarizability (β o) has increased up to 5979.99 au. • Superalkalis doping remarkably tunned the NLO response of all complexes. • Electronic excitation between superalkali and nanocluster is responsible for enhancement of NLO response. In the current study, the effect of superalkalis (Li 3 O, Na 3 O, and K 3 O) doping over bowl shaped silicon carbide (b- SiC) for geometrical, electronic and nonlinear properties has been investigated using DFT theory. The results revealed that doped b- SiC nanoclusters possess high thermodynamic stability as revealed from interaction energy up to −165.85 kcal/mol. The frontier molecular orbitals illustrate the occupation of electronic density in orbitals. Natural bond orbital charge analysis confirms the charge transfer from superalkalis to the b- SiC nanocluster. Furthermore, the electronic properties are rationalized from total density of states spectra. The highest first hyperpolarizability value (5979.99 au) is observed for isomer O of K 3 O@ b- SiC complexes. The electronic excitation is analyzed through UV–VIS analysis. Two-level model describing the internal factors responsible for enhancement of NLO response is also studied. The present work gives a guideline for the synthesis of nonlinear optical materials with greater efficiencies which can be used as building blocks in the modern world of optoelectronics. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new 1,8-naphthalimide based fluorescent probe NS was synthesized by single step imidation reaction. • Probe NS displayed AIEE characteristics with remarkable red-shifted J-aggregates. • Sensing of NB was attributed to J-aggregates formation of probe NS. • Probe exhibited highly selective fluorometric detection of nitrobenzene (NB) down to nanomolar level. A new naphthalimide-based fluorescent probe NS with exceptional J-aggregates based aggregation-induced emission enhancement (AIEE) properties was rationally synthesized through a single-step imidation reaction. Probe NS exhibited excellent AIEE properties in aqueous media through the formation of J-aggregates with remarkable red-shift. The AIEE active probe NS was used for selective and sensitive detection of nitrobenzene (NB) based on fluorescence quenching response. Formation of J-aggregates was assessed through fluorescence titration. These J-aggregates contributed significantly to produce favorable interaction between probe NS and NB. The highly selective fluorescence detection of NB was accredited to the adjustable smaller size of NB that can easily penetrate into interstitial spaces of probe molecules. Ability of sensor to detect NB in solid state was also accomplished through solid state fluorescence spectroscopy. Nature of interaction and sensitivity of probe NS for NB has also been investigated through 1H NMR titration and density functional theory (DFT) including non-covalent interaction (NCI), quantum theory of atom in molecule (QTAIM), electron density differences (EDD), frontier molecular orbitals (FMO) and density of states (DOS) analysis. Advantageously, probe exhibited colorimetric and vapor phase detection of NB. Moreover, probe was quite sensitive for the trace detection of NB in real samples. [ABSTRACT FROM AUTHOR]

• Synthesis of new Sulfonamide-isatin based scaffolds to incorporate first row metals. • Molecular docking to find a best docking pocket for COVID-19 protein. • Online network pharmacology to find a best target for Alzheimer and carbonic anhydrase-II related gene targets. • Characterization with most promising analytical techniques and DFT based studies. • In vitro enzyme inhibition and antimicrobial profiling of new compounds. A series of sulfonamide and isatin based Schiff bases, (S1) and (S2), and their metal (Co2+, Ni2+, Cu2+ and Zn2+) complexes (1)-(8) were synthesized and characterized by spectroscopic (UV, IR, MS, 1H and 13C-NMR), elemental, magnetic and physical techniques. The non-electrolytic character of Co2+, Ni2+, and Zn2+ compounds and electrolytic nature of Cu2+ was established by their conductance studies. The energies of Frontier Molecular Orbitals (FMOs) were also used to explore various global and quantum chemical qualities. To find the activity and molecular targets in curing Alzheimer's Disease (AD) and Carbonic Anhydrase II (CA-II) inhibition, Network Pharmacology modeling was used. The prospective targets were predicted using the Swiss Target PredictionR online facility. The Gene CardsR database has been used to find genes linked to AD and CA-II. We also conducted Gene OntologyR (GO) analysis on the intersecting genes targets on active targets of synthesized compounds by DAVID (Database for Annotation, Visualization and Integrated Discovery) Bioinformatics Services using the CytoscapeR program. The in vitro enzyme inhibition assays were done against protease, amylase, acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) while their antimicrobial studies were performed against pathogenic bacterial and fungal species. The antioxidant values, evaluated as 2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing assay power (FRAP) (%) ranged between 51.0±0.11-68.1±0.11% with IC 50 ranging 146.84-196.08 µL/mol. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Stilbene-based sensor 1 was synthesized and characterized. • The AIEE active fluorescent sensor displayed a significant red shift that was attributed to J -aggregates formation. • Sensor 1 was highly selective and sensitive for solution and vapor phase detection of nitrobenzene (NB). • Sensor 1 was employed for the detection of moisture in organic solvent. • Sensor was used for contact mode identification and rapid detection of nitrobenzene in real samples. • DFT studies were performed to investigate mechanism and to further evaluate type of non-covalent interactions. A unique π-electron rich stilbene-based sensor with significantly enhanced red-shifted fluorescence emission has been synthesized via a Mizoroki-Heck cross-coupling reaction. The strong fluorescence properties of stilbene derivative as a potential fluorescent sensor have been investigated for sensitive and selective detection of hazardous and threatening nitrobenzene (NB) in both solution and vapor phase. The fluorescence emission intensity of stilbene sensor 1 at 474 nm was quenched upon interaction with NB. The fluorescence quenching was attributed to the combined effect of dominant smaller and adjustable size of NB and photo-induced electron transfer (PET) process. Stilbene sensor 1 is the first active bathochromic shifted fluorescent sensor with AIEE property was developed for both solution and vapor phase detection of NB. Possible interactions of stilbene sensor 1 with NB was evaluated by UV– vis., fluorescence, density functional theory (DFT) calculations, and 1H NMR titration experiment. Additionally, non-covalent interaction (NCI), Frontier molecular orbitals (FMOs) and interaction energy were studied by using Gaussian 09 software. Moreover, test strips were fabricated to accomplish contact mode detection of NB. Further, stilbene sensor 1 was successfully applied for trace detection of NB in real water samples. [ABSTRACT FROM AUTHOR]

• Synthesis of derivatives is done through Suzuki-Miyaura coupling reaction. • Structures were analyzed through different spectroscopic techniques. • The experimental results show good agreement with theoretical results. • NLO and electronic properties were also studied. In this study, new arylated derivatives of pyridine named as 6-(4-tertbutylphenyl)-nicotinaldehyde (TBPNA) and 6-(4-hydroxyphenyl)-nicotinaldehyde (HPNA) were synthesized by Suzuki Miyaura C C coupling approach. The structures of newly synthesized compounds were authenticated by spectroscopic techniques like FT-IR, UV-Vis, and 1H-NMR. Furthermore, the structural features of TBPNA and HPNA were explored by using the single-crystal X-ray diffraction technique (SC-XRD) showing monoclinic crystal structure and P2 1 /c space group for both compounds. For a comprehensive study of the compounds, a computational quantum chemical study is also performed by using the density functional theory (DFT). The said compounds were optimized using the B3LYP method and a 6-311++G(d, p) basis set. The comparison of theoretical (DFT) and experimental (SC-XRD) data on structural parameters displayed good agreement. Frontier molecular orbital (FMO), natural bond orbital (NBO), the molecular electrostatic potential (MEP), and time-dependent density functional theory (TD-DFT) were also performed at the B3LYP/6-311++G(d,p) level of theory to get complete insights into electronic communications, intramolecular charge transfer (ICT) process, electronic transition and oscillation strength. The optoelectronic and non-linear optical (NLO) responses of the synthesized compounds were determined by computing the total dipole moment (μ tot), average polarizability ⟨ α ⟩, and the first hyperpolarizability (β tot) at different functional(s) such as HF, M06, M062X, CAM-B3LYP, LC-BLYP, and B3LYP, paired with the 6-311++G(d,p) basis set. The B3LYP method exhibited the highest values of ⟨ α ⟩ and (β tot) for HPNA and TBPNA , which were found to be many times higher than the value of urea (⟨α⟩ = 34.055 a.u., β tot =90.527 a.u.), used as a standard NLO material. [Display omitted] [ABSTRACT FROM AUTHOR]

Making contribution to the development of novel photovoltaic materials for solar cell applications, we rationally developed six novel vinylbenzene based planar donor-π-acceptor (D-π-A) compounds. Optoelectronic properties of developed molecules are determined using frontier molecular orbital (FMO), UV–Visible, density of state (DOS), transition density matrix (TDM) heat map, open circuit voltage (Voc), binding energies (E b), reorganization energy of electron (λ e), hole (λ h), charge transfer analysis and compared with reference DVB-T-ID. Donor group modifications effectively contributed to augment photovoltaic features in all developed compounds. Developed molecules are found with reduced energy gap (2.566–1.805 eV), broaden absorption wavelength (548.09–800.36 nm) and small transition energy (2.262–1.549 eV) as compared to reference DVB-T-ID values 2.819 eV, 492.84 nm and 2.515 eV respectively. The developed molecules have proficient hole and electron transfer mobilities and can serve as best candidate when blended with PC 61 BM film. Optoelectronic features of all developed molecules especially D5 is ascertained eye-catching as compared to DVB-T-ID , hence recommended for future solar cell applications. [Display omitted] • Six vinylbenzene based planar D-π-A photovoltaic compounds are designed by donor group modifications. • The optoelectronic properties were studied in detail using DFT and TDDFT calculations. • FMO, UV–Visible, DOS, ODOS, TDM, Voc, reorganization energy of electron and hole, binding energy and charge transfer analysis are performed. • All vinylbenzene based investigated molecules exhibited remarkable optoelectronic properties. • Investigated molecules are recommended for future solar cell applications. [ABSTRACT FROM AUTHOR]

• Synthesis of novel compounds by using synthetic approach. • Characterization of novel compounds were done through UV–Vis and Hirshfeld surface (HS) analysis. • Frontier molecular orbital energies and MEPs were calculated. • Exploration of NLO properties were performed. Herein, two new cobalt and manganese-based polymers named as catena‑Poly[[diaquabis(4-nitrobenzoato-κO1)cobalt(II)]-µ-pyrazine-κ2N:Nʹ] (COPNO2) and catena‑Poly[[diaquabis(4-nitrobenzoato-κO1)manganese(II)]-µ-pyrazine–κ2N:Nʹ] (MNPNO2) were synthesized. The crystal structure of COPNO2 and MNPNO2 was determined and explored by X-rays diffraction method. O H ⋯ O, C H ⋯ π, N O ⋯ π, and π ⋯ π stacking interactions were the key aspects of the crystal packing of COPNO2 , whereas for MNPNO2 , O H ⋯ O, C H ⋯ π, and π ⋯ π stacking interactions were the key aspects of the crystal packing. The Hirshfeld surface (HS) studies were accomplished for further investigation of the intermolecular interactions. In addition to that, density functional theory (DFT) computations for COPNO2 and MNPNO2 had been carried out at M06 functional, to obtain optimized geometries and double-check the experimental results. Moreover, DFT calculations at the M06 level manifest excellent correlation with the experimental data, which validates the clarity of cobalt and manganese-based polymers. Frontier molecular orbital (FMO) findings were explored to describe nonlinear optical (NLO) properties. The energy gap of COPNO2 was 0.81 eV, while MNPNO2 was examined as 2.16 eV. The global reactivity parameters of COPNO2 and MNPNO2 were determined from the FMO energies. The global reactivity parameters showed that COPNO2 and MNPNO2 have the more donating ability. The NLO results of MNPNO2 (β tot = 1259.17178 a.u.) were observed better than COPNO2 (β tot = 34,678.44833 a.u.). We propose that this synergistic (experimental-computational) study of COPNO2 and MNPNO2 may deliver new ways for its exploitation as NLO material for hi-tech applications. [ABSTRACT FROM AUTHOR]

• Synthesis of novel thiosemicarbazones by using furfural and substituted thiosemicarbazide. • Characterization of novel compounds were done through UV–Vis, IR and NMR spectroscopy. • Natural bonding orbital (NBO) properties indicated the stability of compounds. • Frontier molecular orbital energies and MEPs were calculated. • Exploration of NLO properties were performed. A facile condensation reaction between thiosemicarbazide and furfural was accomplished to synthesize thiosemicarbazone derivatives: TMOH, FMOH, TMEH, FMEH, DCFH and DCMH with good yields as 73%, 70%, 72%,71%, 74% and 74%, respectively. They were characterized by spectroscopic techniques as UV–Vis, FT-IR, 1H and 13CNMR. Furthermore, density functional theory (DFT) analysis was performed by applying M06 level with 6–311G(d,p) basis set for geometry optimization, natural bond orbitals (NBOs), linear and nonlinear optical (NLO) and vibrational analyses. Time-dependent DFT applying M06/6–311G(d,p) level of theory was used for computing frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) and UV–Vis analyses. Experimental values of vibrational wave number and λ max values were seen in good correspondence with the DFT-based results. NBO investigation revealed that title compounds were found with prominent hyper-conjugative interactions having stabilization energies as 57.72, 62.66, 59.95, 58.54, 63.59 and 45.6 kcal/mol , respectively, which are probably the main reasons for their stability. The descending order of E gap was found as DCMH > DCFH > TMOH > TMEH > FMEH > FMOH. Therefore, FMOH , exhibiting the smallest energy gap of 4.416 eV , can be regarded as an efficiently polarized structure, possessing a high capacity for electron transfer. MEP analysis describes the involvement of various reaction sites in chemical reactivity, at different portions of spread electronic cloud over the molecule. The decrease in values of 〈 α〉 for title compounds are found as DCFH > DCMH > FMOH > TMOH > FMEH > TMEH. Moreover, β tot values are found with this order DCFH > DCMH > TMOH > TMEH > FMEH > FMOH. It can be seen that DCMH exhibits a larger NLO response with 〈 α〉 and β tot figured as 300.51 and 2614.07 a.u. , respectively. [ABSTRACT FROM AUTHOR]

• Rare electron-rich hydrazinylthiazoles were synthesized. • XRD, 1H NMR, 13C NMR, FT-IR and HRMS were performed for the characterization. • Computational study was done at M06/6–311G(d,p) level. • Comparative study reveals a good agreement between experimental and DFT results. • NBO, FMO and NLO analysis were calculated. Rare electron-rich 1-(2-{2-[(aryl)methylidene](R-hydrazinyl}-4-methyl-1,3-thiazol-5-yl)ethan-1-ones [ArCH NN(R)C 3 NS(Me)(COMe); Ar = 2-, 3- or 4-MeOC 6 H 4 , R = H, n-C 5 H 11 , CH 2 Ph) were synthesized (70–77%) and characterized (FTIR, HRMS and 1H-/13C NMR spectroscopy). In one case (Ar=3-MeOC 4 H 4 , R = H), the structure was verified by single crystal X-ray diffraction. The observed geometries are true minima, based on M06/6–311G(d,p) level DFT calculation comparisons with experimental data. Calculations were used to extract natural bond orbital (NBO) analyses and predicted non-linear optical (NLO) properties. For comparison, calculated UV–Vis absorptions and frontier molecular orbitals (FMO) analysis were computed using TD-DFT/M06/6–311G(d,p) approaches. The NBO analysis concludes that prolonged hyperconjugation and strong ICT exist in all the entitled compounds, which stabilizes the systems and also offers key evidence of charge transfer/NLO properties. Global reactivity parameters revealed chemical hardness in all molecules and efficient electron donating ability. Calculated band gaps (Egap) of 4.41–4.42 eV were realized while the compound, with all species showing high polarizability. The 4-MeOC 6 H 4 , -CH2Ph (Ar,R) compound had the highest calculated values of first hyperpolarizability (βtot), 2975.06 (a.u) and second hyperpolarizability (<γ>) (2.42 × 105). However, our X-ray results suggest that a centro-symmetric space group is favoured, unvalidating second-order NLO properties studies. [Display omitted] [ABSTRACT FROM AUTHOR]

Recently, syntheses and quantum chemical insights in the structures and properties of crystalline organic compounds have attracted significant attention of the scientific community. In the current work we report the synthesis of two arylsulfonylated 2-amino-6-methylpyrimidin derivatives, A and B. X-ray diffraction technique confirmed the structures of both compounds. The single-crystal analysis showed the presence of various non-covalent interactions that are responsible for their structural stabilities. Theoretical calculations of A and B were performed at the B3LYP/6–311++ G (d,p) level. The calculated structures of both compounds were found to be in good agreement with the experimentally reported structural parameters. Frontier molecular orbital (FMO) analysis showed that employing different moieties to bind with the 2-amino-6-methylpyrimidin-4-ol group causes certain changes to the FMOs energies and energy gaps, thus affecting the stability, reactivity, and other properties of the resulting compounds. The Natural Bond Order (NBO) analysis showed high stabilization energies within the molecules of both compounds. The calculated global reactivity parameters (GRP) confirmed noticeable stability of both compounds, showing the compound B to be more stable than the compound A. • Synthesis of two arylsulfonylated 2-amino-6-methylpyrimidin derivatives reported. • Various non-covalent interactions responsible for their structural stabilities. • Calculated structures in good agreement with the experimentally reported. • NBO analysis showed high stabilization energies within the molecules of both compounds. • Global reactivity parameters confirmed noticeable stability of both compounds. [ABSTRACT FROM AUTHOR]

• Synthesis of mono- and bis-Schiff base ligands of 3,5-diamino-1,2,4-triazole along with their transition metals complexes. • Experimental (IR, UV-Vis, 1HNMR, 13CNMR, ESI-MS) and computational characterization at B3LYP/6-311G(d.p) was done. • Thermal stability and fluorescence properties of compounds were evaluated. • In vitro evaluation of the synthesized ligands and their corresponding 3 d -metal complexes against five pathogenic bacterial species. • Enzyme inhibitory evolution of compounds against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes. The aim of this project was to introduce novel bioactive compounds through the design and synthesis of two mono-Schiff bases, 4- [(5-amino-1H-1,2,4-triazol-3-yl)imino]methylbenzene-1,3-diol (L1) and 2- [(5-amino-1H-1,2,4-triazol-3-yl)imino]methyl}-6-methoxyphenol (L2) and one bis-Schiff base, 2,2′-{1H-1,2,4-triazole-3,5-diylbis [nitrilomethylylidene]}bis(6-methoxyphenol) (L3) together with their complexes of transition metals [VO(IV), Cr(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)]. The molecular structures of as-synthesized Schiff bases were explicitly confirmed by physical, spectral, analytical and computational studies. Quantum chemical calculations based on density functional theory (DFT) were performed at B3LYP/6-311+G(d.p) level to explore the optimized geometrical structures, molecular electrostatic potential (MEP), Mulliken atomic charges (MAC) and frontier molecular orbital (FMO) analysis of the as-synthesized ligands. The FMO energy gaps were rationalized to be 0.162, 0.158 and 0.138 eV for ligands (L1), (L2) and (L3) , respectively which can efficiently polarize their chemical structures. As-synthesized metal complexes have good agreement with their purposed structures with octahedral geometry except vanadium complexes, which have square pyramidal geometry. As-synthesized compounds were also evaluated through thermogravimetry and fluorescence analysis. Additionally, the compounds were also scrutinized for antibacterial activity against five bacterial strains (Halomonas halophila, Chromohalobacter israelensis, Escherichia coli, Chromohalobacter salexigens and Halomonas salina) and enzyme inhibition bioassay against butyrylcholinesterase (BChE) and acetylcholinesterase (AChE). The results showed that the complexes (15) and (1) were the most active inhibitors of BChE and AChE enzymes with 94.60% and 90.90% activity, respectively. Moreover, all the compounds also exhibited significant antibacterial activity. It has been found that the metal complexes displayed more biological activity in contrary to parent ligands as a result of chelation. [Display omitted] [ABSTRACT FROM AUTHOR]