FMO Analysis Research Articles

Third-order nonlinear response of a novel organic acetohydrazide derivative: Experimental and theoretical approach

A novel nonlinear optical (NLO) organic material of N'-[(E)-(5-bromofuran-2-yl)methylidene]-2-(6-chloropyridin-3-yl)acetohydrazide (BCA) was synthesized by reflux method. The synthesized material was characterized using various analytical techniques, including spectroscopic methods (NMR, FTIR, PXRD). The UV–Vis absorption spectrum of BCA was recorded in different solvents. A strong absorption peak was observed in the 280–350 nm range, indicating its potential for UV-based optoelectronic applications. BCA shows good NLO responses (αCT, βCT, γCTvalues) with different solvents. The dielectric measurements were performed using impedance spectroscopy with varying temperatures as a function of frequency. Thermal stability of the material was evaluated using thermogravimetric analysis, indicating high thermal stability up to 153.28°C. The FMO, MEP, and NBO analyses were implemented using density functional theory (DFT) calculations to investigate the BCA molecule's electronic structure and charge distribution. The topology studies were carried out using the QTAIM and NCI to understand the structure's chemical bonding and intermolecular interactions and the structure's chemical bonding and intermolecular interactions. NLO properties of the BCA material were investigated using the Z-scan technique with a continuous wave (CW) laser, revealing a strong third-order nonlinear susceptibility (χ(3)) value of 2.44 × 10−6 e.s.u. and potential optical limiting behavior (OL threshold = 3.437 × 103 Wcm−2). The TD-HF method performed the calculated molecular static and dynamic of NLO parameters with frequency. The computed γ value of 6.2 × 10−36 e.s.u. was found to be consistent with the experimental value. The results of this study recommend that the synthesized hydrazide derivative material has potential NLO applications.

Covalent Triazine Framework C6N6 as an Electrochemical Sensor for Hydrogen-Containing Industrial Pollutants. A DFT Study

Industrial pollutants pose a serious threat to ecosystems. Hence, there is a need to search for new efficient sensor materials for the detection of pollutants. In the current study, we explored the electrochemical sensing potential of a C6N6 sheet for H-containing industrial pollutants (HCN, H2S, NH3 and PH3) through DFT simulations. The adsorption of industrial pollutants over C6N6 occurs through physisorption, with adsorption energies ranging from -9.36 kcal/mol to -16.46 kcal/mol. The non-covalent interactions of analyte@C6N6 complexes are quantified by symmetry adapted perturbation theory (SAPT0), quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) analyses. SAPT0 analyses show that electrostatic and dispersion forces play a dominant role in the stabilization of analytes over C6N6 sheets. Similarly, NCI and QTAIM analyses also verified the results of SAPT0 and interaction energy analyses. The electronic properties of analyte@C6N6 complexes are investigated by electron density difference (EDD), natural bond orbital analyses (NBO) and frontier molecular orbital analyses (FMO). Charge is transferred from the C6N6 sheet to HCN, H2S, NH3 and PH3. The highest exchange of charge is noted for H2S (-0.026 e-). The results of FMO analyses show that the interaction of all analytes results in changes in the EH-L gap of the C6N6 sheet. However, the highest decrease in the EH-L gap (2.58 eV) is observed for the NH3@C6N6 complex among all studied analyte@C6N6 complexes. The orbital density pattern shows that the HOMO density is completely concentrated on NH3, while the LUMO density is centred on the C6N6 surface. Such a type of electronic transition results in a significant change in the EH-L gap. Thus, it is concluded that C6N6 is highly selective towards NH3 compared to the other studied analytes.

Synthesis, crystal structure, DFT calculations, and Hirshfeld surface analysis of an NNN pincer type compound

The novel benzamide derivative NNN pincer type, N,N'-(azanediylbis(2,1-phenylene))bis(3-chlorobenzamide) (H3L), was synthesized from bis(2-nitrophenyl)amine starting material. The pincer ligand was characterized by 1H NMR, 13C NMR, COSY, HMQC, and FT-IR techniques. The geometry of pincer ligand was also confirmed by a single-crystal X-ray diffraction analysis. Structural analysis demonstrate that H3L is monoclinic and space group P21/n with Z = 4. It was find out the molecular conformation of the structure is promoted by intramolecular (NH⋅⋅⋅O, NH⋅⋅⋅N, and CH⋅⋅⋅O) and intermolecular (N(2)-H(2)⋅⋅⋅O(2)i, symmetry code (i) = 1/2 + x, 3/2-y, 1/2 + z) hydrogen bonds. The theoretical study of H3L was performed in the gaseous phase by B3LYP/6-311G(d,p) method to determine the structural properties of the title molecule, as a consequence the obtained data showed that the considerable agreement between the experimental and theoretical results. The reactivity and stability of the molecule were evaluated by calculating the HOMO–LUMO energy gap which was found as 6.5163 eV. In addition, FMO, NBO, NLO, DOS, RDG, MEP surface, and Mulliken atomic charge analyses were carried out. Hirshfeld surface analysis and two-dimensional fingerprint plots were investigated and the obtained data exposed that the most significant contributions to the crystal packing are from C···H/H···C (33.2%), H···H (31.5%), and H···Cl/Cl··H (18.9%) contacts. Furthermore, the molecular docking studies were performed to reveal the binding affinity between the title compound and the main protease (6LU7) of COVID-19 coronavirus.

(E)-4-((4-chlorobenzylidene)amino)-N-(thiazole-2yl) benzenesulfonamide: Synthesis, characterization and electronic structure theory and docking studies

Spectroscopic methods (NMR, UV–vis) were utilized to get an understanding of the molecular structure of the (E)-4-((4-chlorobenzylidene)amino)-N-(thiazole-2yl) benzenesulfonamide (4CLBTH). The DFT/B3LYP/cc-pVDZ, were used in the theoretical study of the compound. Calculations using DFT can produce geometrical parameters such as bond lengths and bond angles. The GIAO method was utilized in DMSO to calculate the 1H and 13C NMR for TMS. These results were then compared to the observed data. The UV–Vis spectrum of 4CLBTH was computed by using the B3LYP with the cc-pVDZ basis set. Using theoretical calculations, an investigation into the FMO analysis and the MEP were carried out. The theoretical findings and the experimental findings are in reasonable agreement with one another. The molecular docking was investigated by the autodock suite and visualised using the discovery studio visualizer. The multiwfn software was used to calculate the wavefunction studies.

Organocatalytic Enantioselective Thermal [4 + 4] Cycloadditions.

Chiral eight-membered carbocycles are important motifs in organic chemistry, natural product chemistry, chemical biology, and medicinal chemistry. The lack of synthetic methods toward their construction is a challenge preventing their rational design and stereoselective synthesis. The catalytic enantioselective [4 + 4] cycloaddition is one of the most straightforward and atom-economical methods to obtain chiral cyclooctadiene derivatives. We report the first organocatalytic asymmetric [4 + 4] cycloaddition of 9H-fluorene-1-carbaldehydes with electron-deficient dienes affording cyclooctadiene derivatives in good yields and with excellent control of peri-, diastereo-, and enantioselectivities. The reaction concept is based on the aminocatalytic formation of a polarized butadiene component incorporated into a cyclic extended π-system, with restricted conformational freedom, allowing for a stereocontrolled [4 + 4] cycloaddition. FMO analysis unveiled that the HOMO and LUMO of the two reacting partners resemble those of butadiene. The methodology allows for the construction of cyclooctadiene derivatives decorated with various functionalities. The cyclooctadienes were synthetically elaborated, allowing for structural diversity demonstrating their synthetic utility for the formation of, for example, chiral cyclobutene- or cyclooctane scaffolds. DFT computational studies shed light on the reaction mechanism identifying the preference for an initial but reversible [4 + 2] cycloaddition delivering an off-cycle catalyst resting state, from which catalyst elimination is not possible. The off-cycle catalyst-bound intermediate undergoes a retro-[4 + 2] cycloaddition, followed by a [4 + 4] cycloaddition generating a cycloadduct from which catalyst elimination is possible. The reaction pathway accounts for the observed peri-, diastereo-, and enantioselectivity of the organocatalytic [4 + 4] cycloaddition.

Synthesis, crystal structure, DFT, Hirshfeld surface analysis, energy framework, docking and molecular dynamic simulations of (E)-4-(4-methylbenzyl)-6-styrylpyridazin-3(2H)-one as anticancer agent

In this work, a novel crystal, (E)-4-(4-methylbenzyl)-6-styrylpyridazin-3(2H)-one (E-BSP) was synthesized via Knoevenagel condensation of benzaldehyde and (E)-6-(4-methoxystyryl)-4,5-dihydropyridazin-3(2H)-one. The molecular structure of E-BSP was confirmed by using FT-IR, 1H-NMR, 13C-NMR, UV-vis, ESI-MS, TGA/DTA thermal analyses and single crystal X-ray diffraction. The DFT/B3LYP methods with the 6-311++G(d,p) basis set were used to determine the vibrational modes over the optimized structure. Potential energy distribution (PED) and the VEDA 4 software were used to establish the theoretical mode assignments. The same approach was used to compute the energies of frontier molecular orbitals (HOMO-LUMO), global reactivity descriptors, and molecular electrostatic potential (MEP). Additionally, experimental and computed UV spectral parameters were determined in methanol and the obtained outputs were supported by FMO analysis. Molecular docking and molecular dynamics (MD) simulation analyses of the E-BSP against six proteins obtained from different cancer pathways were carried out. The proteins include; epidermal growth factor receptor (EGFR), Estrogen receptor (ERα), Mammalian target of rapamycin (mTOR), Progesterone receptor (PR) (Breast cancer), Human cyclin-dependent kinase 2 (CDK2) (Colorectal cancer), and Survivin (Squamous cell carcinoma/Non-small cell lung cancer). The results of the analyses showed that the compound had less binding energies ranging between −6.30 to −9.09 kcal/mol and formed stable complexes at the substrate-binding site of the proteins after the 50 ns MD simulation. Therefore, E-BSP was considered a potential inhibitor of different cancer pathways and should be used for the treatment of cancer after experimental validation and clinical trial. Communicated by Ramaswamy H. Sarma

Copper(II) chelates derived from an N,N,O-tridentate 2-pyridinecarboxaldehyde-N4-phenylsemicarbazone: Synthesis, spectral aspects, crystal structure, FMO and NBO analysis

Seven novel Cu(II) complexes [Cu(HPySc)Cl2] (1), [Cu2(PySc)2(NO3)2]·H2O (2), [Cu(HPySc)(SO4)]·½H2O (3), [Cu2(PySc)2(OAc)2]·CH3OH (4), [Cu2(PySc)2Br2]·H2O (5), [Cu(PySc)(NCS)]·2H2O (6) and [Cu2(PySc)2(N3)2] (7) with 2-pyridinecarboxaldehyde-N4-phenylsemicarbazone (HPySc) have been prepared and characterized using different analytical and spectroscopic techniques. The complex 6 is expected to be square planar while the other complexes are expected to be square pyramidal arrangement, among these, the geometry of complex 4 has been conformed by single crystal XRD study that it is a dimer and adopts distorted square pyramidal geometry around copper(II) centre. All the complexes are found to be paramagnetic and non-conductive in nature. The semicarbazone ligand is coordinated in neutral form in two of the complexes and in ionic form in others. DFT/B3LYP/6-311g**/LANL2DZ computations of the ligand HpySc (PyCHNNCONHPh) and seven Cu(II) complexes were performed to analyze the FMOs and important electron delocalizations that existed in each compound. Molecular stability and bond strengths have been investigated by applying natural bond orbital (NBO) analysis. All the complexes are more stable than the semicarbazone and the complex 2 is the most electronically stable (-5.160 eV) among the complexes. Furthermore, the semicarbazone is the hardest and complex 5 is the softest than all complexes due to the η values. The calculated energy gap between HOMO and LUMO energies show the variations of nucleophilic and electrophilic reactivity regions in the semicarbazone and in complexes 1-7.

Synthesis, characterization and biological evaluation of novel 2-aminopridinium nicotinate invitro antifungal, insilico ADME and molecular docking studies

Prospective anti-fungal compound 2-amino pyridinium nicotinate (2APNA) was synthesized and characterized using FT-IR, FT-Raman and UV-visible analysis. To validate the molecular structure, a single X-ray diffraction study was performed. The structure of the molecule was optimized and the structural parameters are determined by DFT method with B3LYP/6-31G(d,p) basis set. The presence of functional groups in 2APNA crystal is confirmed by FT-IR and FT-Raman spectral analysis. On contrary, FMO analysis, global chemical reactivity descriptors and natural charge analysis were studied. Molecular stability and bond strength have been probe by executing NBO analysis. The Fukui and electrostatic potential plot analysis can provide information about the molecules electrophilic and nucleophilic locations. UV–Vis spectrum was predicted by TD-DFT method in gaseous phase and compared with the experimental spectrum for displaying the intricate electronic transitions in the compound. The interactions within the 2APNA molecule was investigated via RDG analysis. To investigate the ligand-protein interaction, a molecular docking simulation was used, whereas drug likeness and ADMET analysis was used to determine the biological characteristics of the title molecule. Antifungal testing was performed to investigate the compound's efficacy against fungicidal strains.

N-(p-Toluenesulfonyl)-1-(4′-acetylphenoxy)acrylimidate: Synthesis, Crystal Structure and Theoretical Studies

The formation of N-sulfonyl-1-aryloxy acrylimidate is described, for the first time, from a consecutive process, which involves a CuAAC reaction, a ketenimine formation and subsequent rearrangement between an aryl propargyl ether and a sulfonyl azide. The structure of this newly synthesized compound was analyzed by NMR spectra and unambiguously established by X-ray analysis. In addition, theoretical calculations, which included a Hirshfeld surface, FMO, QTAIM and NCI indices analysis, corroborated the formation of π-π stacking interactions among aromatic rings, as well as C-H···O interactions between vinyl hydrogens with ketone carbonyl oxygen.

Theoretical exploration on structures, bonding aspects and molecular docking of α-aminophosphonate ligated copper complexes against SARS-CoV-2 proteases.

Recent years have witnessed a growing interest in the biological activity of metal complexes of α-aminophosphonates. Here for the first time, a detailed DFT study on five α-aminophosphonate ligated mononuclear/dinuclear CuII complexes is reported using the dispersion corrected density functional (B3LYP-D2) method. The electronic structures spin densities, FMO analysis, energetic description of spin states, and theoretical reactivity behaviour using molecular electrostatic potential (MEP) maps of all five species are reported. All possible spin states of the dinuclear species were computed and their ground state S values were determined along with the computation of their magnetic coupling constants. NBO analysis was also performed to provide details on stabilization energies. A molecular docking study was performed for the five complexes against two SARS-CoV-2 coronavirus protein targets (PDB ID: 6LU7 and 7T9K). The docking results indicated that the mononuclear species had a higher binding affinity for the targets compared to the dinuclear species. Among the species investigated, species I showed the highest binding affinity with the SARS-CoV-2 Omicron protease. NPA charge analysis showed that the heteroatoms of model species III had a more nucleophilic nature. A comparative study was performed to observe any variations and/or correlations in properties among all species.

Regiocontrolled Rh(III)-catalyzed C[sbnd]C coupling/C[sbnd]N cyclization mediated by distinctive 1,2-migratory insertion of gem‑difluoromethylene allenes: Reaction development and mechanistic insight

By developing gem‑difluoromethylene allenes as viable partners, regiocontrolled Rh(III)-catalyzed redox-neutral CC coupling/CN cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of a Z-configured monofluoroalkene functionality, in which either (hetero)aromatic or vinylic amides were found to be compatible. Integrated experimental and computational mechanistic studies revealed that a tandem regioselective allene 1,2-insertion/β-H elimination/hydrogen transfer/oxidative addition/cyclization/cis-β-F elimination involving an unconventional Rh(III)-Rh(I)-Rh(III) catalytic cycle accounts for the established transformation. Through further FMO analysis and IGMH maps, a non-covalent weak interaction network between the gem‑difluoromethylene part and the OPiv moiety was rationally defined for the unconventional and specific regioselectivity control.

Electronic, geometrical and photophysical facets of five coordinated porphyrin N-heterocyclic carbene transition metals complexes: A theoretical study

In the realm of dye sensitized solar cells (DSSCs), the 3d transition metals as photosensitizers are scarcely studied. In the present work, electronic structures, FMO, MEP surfaces, NBO analysis, energetics and photophysical properties of earth abundant metals (Mn, Fe and Co) based metalloporphyrins coordinated with NHC-carbene have been explored by using DFT and TDDFT calculations. According to formation energies and energy decomposition analysis (EDA), the cobalt based metalloporphyrins species are found to be more stable while in contrast manganese based species are predicted as more reactive among all. Also, from the ligation point of view, the TPP (meso-tetraphenylporphyrin) ligand forms more steady and rigid coordination as compare to the TTP (meso-tetratolylporphyrin) ligand. FMO analysis also support these observations. NBO and SNO results support the electronic configurations as well as unveil the controversial bonding pattern of NHCcarbon and metal atom and found that there is σ-bonding present between the metal and the NHCcarbon by the overlapping of sp-hybridized orbitals of carbenecarbon and sp/d hybrid orbital of the metal atom. TDDFT results show that the highest light harvesting efficiency (LHE) of all the studied species is found under the range of 360 nm − 380 nm (λ) and this may due to the presence of longer π-conjugations. In-depth investigation of this work may help to design new robust energy harvesting systems for high energy conversion efficiency based on earth abundance metals. Our results are in well agreement with the available experimental findings.

Mechanistic Study on Gold(I)-Catalyzed Unsaturated Spiroketalization Reaction

Abstract: The mechanism of metal-catalyzed spiroketalization of propargyl acetonide is explored by employing DFT with the B3LYP/6-31+G(d) method. Acetonide is used as a regioselective regulator in the formation of monounsaturated spiroketal. The energies of transition states, intermediates, reactants and products are calculated to provide new insight into the mechanism of the reaction. The energetic features, validation of the observed trends in regioselectivity are conferred in terms of electronic indices via FMO analysis. The presence of acetonide facilitates a stepwise spiroketalization as it masks the competing nucleophile, and thus hydroxyl group present exclusively acts as a nucleophile. The vinyl gold intermediate 3 is formed from 2 via activation barrier TS1. This is the first ring formation, which is 6-exo-dig cyclization. The intermediate 3 is converted into allenyl ether 4, which isomerizes to the intermediate oxocarbenium ion 5 via activation barrier TS2. The intermediate 5 cyclizes to 6 via TS3. This is the second ring formation. The intermediate 6 on protodeauration turns into 6,6-monounsaturated spiroketal 7. It is concluded that acetonide as a protecting group serves the purpose, and thus a wide range of spiroketals can be prepared regioselectivity.

Nitrobenzamido substitution on thiophene-3-carboxylate: Electrochemical investigation, antioxidant activity, molecular docking, DFT calculations

A novel nitro containing thiophene derivatives containing have been synthesized. In pharmaceutical chemistry, thiophene derivatives show a biological effect. Due to the promising antimicrobial, analgesic and anti-inflammatory, and antitumor activity, alternative and different approaches have also been one of the main objectives in the field of chemical sciences. Based on the broad range of biological properties of thiophene derivatives, this study aimed to evaluate the antioxidant activity of novel thiophene derivatives and explore the electrochemical features using CV (cyclic voltammetry). The synthesis and characterization of novel benzo[b]thiophone derivatives were confirmed using spectroscopic methods with 1H-NMR, 13C-NMR, FT-IR, and UV-vis. The DFT and TD-DFT computations were conducted to compare the spectroscopic data and then confirm the molecular structures of the compounds 1-3. The FMO and NBO analyses were conducted to estimate the possible reactivity features and key intra-molecular interactions. Last, molecular docking investigations were performed to explore the possible interaction of each compound to human EGFR Kinase.

Impact of Protonation and Hydrogen Bonding Interactions on the Biological Properties of Antibacterial Compound 4-Dimethylaminopyridinium Salicylate Monohydrate: Correlation with Its Precursor Molecules

The hypothetical molecule 4-dimethylaminopyridinium salicylate monohydrate was synthesized and investigated leveraging FT-IR spectra, UV visible, NMR and quantum chemical calculations and also compared with its precursor molecules 4-dimethylamino pyridine and salicylic acid in the present work. To explore the impingement of hydrogen bonding on molecule the geometrical parameters, interaction energies, and vibrational spectra are employed. Natural Bond Orbital analysis indicated the existence of intermolecular hydrogen bonding N–H…O contact, which is mediated by a hyperconjugative interaction between the carbonyl oxygen atom donor and the pyridine ring N–H acceptor. The stretching wavenumber of hydrogen bond donor O–H and hydrogen bond acceptor C–O is red shifted due to elongation in respective bond lengths, according to vibrational analysis. The presence of intermolecular charge transfer from electron-rich pyridine to electron-deficient salicylate is revealed by FMO analysis, and this is corroborated by charge transfer due to excitation. A molecular docking simulation was also executed to better understand the structure-activity relation and further antibacterial tests confirmed that the compound inhibits the bacterial pathogens.

Synthesized thiazole-based hydrazides and their spectral characterization along with biological studies: Promising quantum chemical insights

Hydrazide scaffold is very significant in medicinal and synthetic chemistry. Hydrazides lead to heterocyclic pharmacophores exhibiting substantial physicochemical properties. Synthesis of 2-(2-(arylidene)hydrazinyl)thiazole-4-carbohydrazides (BHTC1-BHTC6) (48–69%), was accomplished through multistep sequence, incorporating variable electronic properties in the arylidene moiety. The structures of the accomplished synthetic design were established via FT-IR, HRMS, 1H and 13CNMR . The α-Amylase study of all new compounds showed percentage inhibition values within the range of 17.78±0.023 to 31.00±0.19 at 50 µg/mL as compared to acarbose (85.56±0.56, at 50 µg/mL). However, the synthesized compounds also exhibited moderate to good protein kinase inhibition as well. The computational analyses were also accomplished for BHTC1-BHTC6 at M06 functional with a 6–31G(d,p) basis set. To elucidate the stability and ICT of the compounds, NBO and FMO analyses were conducted. The synthesized compound BHTC6 displayed the lowest bandgap value, i.e., 4.355 eV among BHTC1-BHTC5. The global reactivity parameters were correlated with their bandgap data and BHTC6 was concluded to express a high value of softness and a low hardness value among entitled compounds. Moreover, UV–Vis analysis indicates that BHTC6 is the most bathochromically shifted among all designed compounds, possessing λmax of 381.534 nm. The aforementioned results reveal that these compounds may prove significant in developing better enzyme inhibitors or antimicrobial agents.

DFT study of super-halogen (Al7) doped carbon nitride (C2N) and its nonlinear optical properties

In this study, density functional theory (DFT) has been employed to conduct a systematic study of a non-linear optical and electrical characteristic of a specific class of carbon nitride (C2N) doped with super-halogen cluster (Al7). The optimization of molecular geometries of pure C2N (A1), single doped Al7@C2N (A2), and double doped 2Al7@C2N (A3) systems and comparison of their NLO properties are carried out at three functionals CAM-B3LYP, B3LYP, and LC-BLYP along with 6-31G basis set. Among these three methods of DFT, the B3LYP method provides the lowest bandgap and highest first hyperpolarizability (βo). The doping of Al7 on C2N significantly enhances the charge transfer characteristics by lowering the bandgap (Eg) from 2.32 eV to 0.99 and 0.95 eV for A1, A2, and A3 systems respectively. βo and dipole moment (μ) also increase remarkably from 1649 to 30221 au and 2.04 to 10.26 D, respectively. Among all the three A1, A2, and A3 systems, A2 system is extraordinarily efficient in HOMO and LUMO energies, Eint, EVI, as well as UV-Vis absorption. A2 exhibits significant absorption in the far-red region, which has been utilized in lasers. TD-DFT calculations along with FMO, DOS, and EDDM analysis were utilized to track down the source of electro-optical and structural property correlations. The mentioned systems, particularly single doped A2 system, have the opportunity to be used as useful NLO material.

Development of non-fused acceptor materials with 3D-Interpenetrated structure for stable and efficient organic solar cells

The modification of end-capped acceptors of a molecule is an efficient strategy for novel solar cells. In this line, we have tailored and explored eight novel molecules for possible application in photovoltaics. Further, a neat and clean light absorption spectrum has been recorded for designed molecules (T1-T8) in the organic solvent. The lower values of excitation energy of novel molecules help in easy excitation and dissociation of excitation in the excited state. Moreover, the mobility in the active layer of electron and hole of solar cell is high, which is seen in T1 to T8 molecules. Overall, the geometric and physiochemical analysis highlights the high performance of tailored molecules of solar cells. The density functional theory (DFT) calculations were used to estimate FMO analysis, Electrostatic-Potential (ESP), Density of States (DOS) graphs, Reorganizational Energy, photovoltaic properties, and charge transmission investigation. Engineered particles have greater and identical optoelectronic properties than synthetic reference molecules. T5 has emerged as the best candidate among all the molecules studied because of its talented photovoltaic properties, which contain the minimum bandgap (1.99 eV), the mobility of electrons, and hole are (λe = 0.0112 eV), (λh = 0.0101 eV), respectively. These materials showed a lower binding energy (Eb = 0.48 eV), and are highly red-shifted in absorption spectrum i.e. 798.55 nm (in gas), while 820.49 nm in chloroform. Moreover, these materials also presented a good value of Open circuit voltage (Voc), which are in the range of 1.26–1.83 V for the designed series (T1-T8), while 1.77 V for the R molecule. Therefore, we highly suggest these materials for the future development of an efficient organic solar cells (OSCs).

Molecular design, electronic structure and optoelectronic properties of vinyl fused monomeric and oligomeric benzothiazoles—A theoretical investigation

The organic semiconductors have apprehended a significant role in flexible, thin-film, electronics with different flavors of applications. They are fabricated into electronic devices to enhance their overall performance and efficiency. Optimizing the optoelectronic properties will improve the performance of the device. In this work, a theoretical investigation has been made on vinyl fused monomeric and oligomeric benzothiazole molecules were presented to propose new organic materials for organic electronics. Moreover, fourteen monomeric and oligomeric benzothiazole molecules designed with donors (-N(CH3)2, -OH) and acceptors (-CN, -CF3) to construct D-π-A frames. The DFT and TDDFT methods with B3LYP/6–31+G(d,p) and B3P86/6–311++G(d,p) basis set were employed to elucidate the optoelectronic properties of the designed molecules. Using these methods, several parameters such as the geometry, polarity (dipole, polarizability hyperpolarizability), FMO analysis, charge transport properties, molecular electrostatic potential (MEP), excited-state properties, and further molecular electronic structure properties of the designed molecules have been computed. The results obtained confirmed that the geometric parameters, HOMO-LUMO gap, ionization potential (IP), electron affinity (EA), reorganization energies (λ), polarizability, hyperpolarizability, and absorption and emission spectra of the designed candidates can be significantly tuned by substitution of different donor-acceptor groups and extending the benzothiazole ring and these compounds can be used to make efficient optoelectronics. The conclusion of the work reveals that -N(CH3)2:-CN and -CN:-OH substituted oligomers demonstrates significant optoelectronic properties which could be used in optoelectronic devices.

Zinc(II) catalyzed synthesis of 2-(4-methoxyphenyl)-5-(2-pyridyl)-1,3,4-thiadiazole: Characterizations, crystal structure, DFT calculation, Hirshfeld surface analysis, and molecular docking analysis

A new compound 2-(4-methoxyphenyl)-5-(2-pyridyl)-1,3,4-thiadiazole (Mppth) has been synthesized and characterized with the aid of IR, NMR, and single-crystal X-ray diffraction techniques. During the reaction, the substituted thiohydrazide got cyclized into the corresponding thiadiazole (Mppth) in the presence of zinc(II) nitrate via loss of H2O. The Mppth crystallizes in an orthorhombic system with space group P 21 21 21. The solid-state structure of Mppth is stabilized via intermolecular hydrogen bonding and π-π interaction between phenyl rings. The intermolecular interactions present in the crystal structure of Mppth are also confirmed with Hirshfeld surface analysis. The geometry optimization has been performed using the DFT method and geometrical parameters thus obtained for the Mppth correlate with the single-crystal X-ray data. The FMO analysis shows a small HOMO and LUMO energy gap of 5.48 eV for Mppth suggesting its potential application as NLO material. The electronic transition from the ground state to the excited state due to a transfer of electrons from the HOMO to LUMO levels is mainly associated with the π→π* transition. Molecular docking studies are also performed against CYP-19 (PDB: 3EQM), JAK2 (PDB: 5AEP), BCL-2 (PDB: 2O2F), and caspase3 (PDB: 1RE1) receptor proteins to obtain insights on anticancer activities of Mppth. The results displayed strong interactions with the receptors with binding energies -10.27, -7.40, -6.28, and -7.27 kcal/mol, respectively. From the docking results, the key binding interactions between the ligand and active site residues of the receptor were identified, which may provide important information for further research on the compound Mppth as anticancer agent.