Chasing Turns and Twists: Unraveling the One-Step Synthesis, Intricate Pathways, and Structural Revelations of N-Aryl Aza-quasi[8]circulenes.

An efficient one-step synthesis of N-Aryl aza-quasi[8]circulenes is reported starting from bis(biaryl)carbazoles. The intermediacy of N-aryl aza[7]helicene is investigated, and the Scholl oxidative cyclization route is invoked here to overcome the large strain during the formation of N-aryl aza-quasi[8]circulenes from N-aryl aza[7]helicene. Notably, this transformation occurs without the need for directing groups and proceeds from a more helical to a less helical pathway. Both the N-aryl aza[7]helicene and N-aryl aza-quasi[8]circulene are confirmed by single crystal X-ray structural analysis. The enantiomers of N-aryl aza[7]helicene are separated by chiral HPLC and analyzed by circular dichroism spectroscopy to investigate their chiroptical properties. However, N-aryl aza-quasi[8]circulene racemizes rapidly. The radical cations generated from aza-quasi[8]circulene through chemical oxidation exhibit broad absorption in the near-IR region and air stability up to 24 h. Optical and electrochemical studies with aza[7]helicene and aza-quasi[8]circulene derivatives highlight their potential in organic electronic devices.

The impact of aromatic π-spacers and internal acceptors in triphenylamine dyes for DSSCs: A DFT approach.

In present work, the influence of internal acceptors and π-spacers on optoelectronic properties for dye-sensitized solar cells (DSSCs) is investigated. The dyes consist of various internal acceptors (A), a triphenylamine donor and π-spacers combined with cyanoacrylic acid acceptor. Density functional theory (DFT) was employed to inspect the dye geometries, charge transport characteristics and electronic excitations. The frontier molecular orbitals (FMOs), highest occupied molecular orbital, lowest unoccupied molecular orbital and HOMO-LUMO energy gap are assisted in the determination of suitable energy levels for electron transfer, electron injection and regeneration of dye. The required photovoltaic parameters like JSC, ΔGreg, ΔGinj, LHE and other associated parameters are presented. The results demonstrate that altering the π-bridge and adding an internal acceptor to the D-π-A scaffold changes the photovoltaic properties and absorption energies. Therefore, the key objective of the current effort is to launch a theoretical groundwork for suitable operational alterations and scheme in creating successful DSSCs.

Optoelectronic design and charge transport properties of Benzodifuran (BDF) isomers for organic electronic devices: DFT/TD-DFT insights.

The primary goal of this work is to provide a comprehensive analysis of the charge transport and optoelectronic characteristics of all the isomers of benzodifuran (BDF) for organic electronic devices in order to suggest qualified materials/candidates for organic photovoltaic devices. Density functional theory (DFT) calculations were performed for all possible isomers of BDF and results are compared with corresponding experimental known isomers. Time Dependent-Density Functional Theory (TD-DFT) is used for the calculation of the absorption and HOMO-LUMO energy levels. To characterize the electronic charge transport state in these isomers, the ionization potentials (IP), reorganization energies (hole and electron), and electron affinities (EA) of all the isomers are investigated. Comparatively, all the BDF isomers are having low electron and hole reorganization energies and hence they can be used in the organic electronic material fabrication.

Analysis of the spectral-luminescence properties of imidazo[1,2-b]pyrido[4,3-e][1,2,4]triazin-6(7Н)-ones.

The article presents a method for the construction of a new tricyclic system of imidazo[1,2-b]pyrido[4,3-e][1,2,4]triazin-6(7Н)-ones based on subsequent reactions of the obtained 1,2-diamino-4-phenylimidazole ethyl ether of 3-methyl-6-phenylimidazo[1,2-b][1,2,4]triazin-2-carboxylic acid with dimethylformamide dimethyl acetal and primary amines. The structures of the obtained compounds were confirmed using the data obtained from 1 Н and 13 С NMR, HRMS, and XRD analyses. We analyzed the dependence of the absorption and photoluminescence spectra on the structure of the compounds obtained using quantum chemistry methods. The theoretical results were compared with the data from a real experiment. The article suggests a range of practical applications for imidazo[1,2-b]pyrido[4,3-e][1,2,4]triazin-6(7Н)-ones.

Coronene-embedded 'super' coumarins.

A non-planar π-enlarged coronene-embedded coumarin achieved via pyranone annulation and its cyanated derivative possess bright orange to red emission in both solution and solid states, with scope for bioimaging applications. The multiple redox states, frontier molecular orbital energy levels and strong cofacial π-stacking ability point towards applications in organic optoelectronics.

Ultrafast Excited State Relaxation Dynamics of New Fuchsine- a Triphenylmethane Derivative Dye.

An all-inclusive investigation of the ultrafast excited state relaxation dynamics of a triphenylmethane derivative molecule, New Fuchsine (NF), using a combined approach of density functional theory (DFT), femtosecond transient absorption spectroscopy (fs-TAS), and photoluminescence spectroscopy is presented in this work. The DFT calculations confirmed the formation of twisted molecular structure in the excited state of NF in ethanol solution with bond rotation of ≈86°. TAS measurements of NF solution exhibited ultrafast ground state-recovery pathway via a conical intersection confirming an ultrafast structural reorientation. On the contrary, TAS measurements of NF thin-film exhibited a longer excited-state lifetime suggesting a hindered molecular twisted state formed as an intermediate step. Photophysical kinetic models are proposed to globally fit the fs-TAS data establishing the twisted intramolecular charge transfer (TICT) state mediated ground state recovery for NF in solution and thin film, respectively. Temperature-dependent photoluminescence study of NF film provided a clear insight into the effect of rotational motion of phenyl rings in NF molecules over the TICT mediated emission.

In-silico strategies for probing chloroquine based inhibitors against SARS-CoV-2.

The global health emergency of novel COVID-19 is due to severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2). Currently there are no approved drugs for the treatment of coronaviral disease (COVID-19), although some of the drugs have been tried. Chloroquine is being widely used in treatment of SARS-CoV-2 infection. Hydroxychloroquine, the derivative of Chloroquine shows better inhibition than Chloroquine and has in vitro activity against SARS-CoV-2 also used to treat COVID-19. To study the interactions of Chloroquine and derivatives of Chloroquine with SARS-CoV-2, series of computational approaches like pharmacophore model, molecular docking, MM_GBSA study and ADME property analysis are explored. The pharmacophore model and molecular docking study are used to explore the structural properties of the compounds and the ligand-receptor (PDB_ID: 6LU7) interactions respectively. MM_GBSA study gives the binding free energy of the protein-ligand complex and ADME property analysis explains the pharmacological property of the compounds. The resultant best molecule (CQD15) further subjected to molecular dynamics (MD) simulation study which explains the protein stability (RMSD), ligand properties as well as protein-ligand contacts. Outcomes of the present study conclude with the molecule CQD15 which shows better interactions for the inhibition of SARS-CoV-2 in comparison to Chloroquine and Hydroxychloroquine.Communicated by Ramaswamy H. Sarma.

Diacetoxy iodobenzene mediated regioselective synthesis and characterization of novel [1,2,4]triazolo[4,3-a]pyrimidines: apoptosis inducer, antiproliferative activities and molecular docking studies.

Prompt and regioselective synthesis of eleven novel [1,2,4]triazolo[4,3-a]pyrimidines 2a-2k, via intramolecular oxidative-cyclization of 2-(2-arylidenehydrazinyl)-4-methyl-6-phenylpyrimidine derivatives 1a-1k has been demonstrated here using diacetoxy iodobenzene (DIB) as inexpensive and ecofriendly hypervalent iodine(III) reagent in CH2Cl2 at room temperature. Regiochemistry of final product has been established by developing single crystal and studied X-ray crystallographic data for two derivatives 2c and 2h without any ambiguity. These prominent [1,2,4]triazolo[4,3-a]pyrimidines were evaluated for human osteosarcoma bone cancer (MG-63) and breast cancer (MCF-7) cell lines using MTT assay to find potent antiproliferative agent and also on testicular germ cells to find potent apoptotic inducing activities. All compounds show significant cytotoxicity, particularly 3-(2,4-dichlorophenyl)-5-methyl-7-phenyl-[1,2,4]triazolo[4,3-a]pyrimidine (2g) was found significant apoptotic inducing molecule, as well as the most potent cytotoxic agent against bone cancer (MG-63) and breast cancer (MCF-7) cell lines with GI50 value 148.96 µM and 114.3 µM respectively. Molecular docking studies has been carried out to see the molecular interactions of synthesized compounds with the protein thymidylate synthase (PBD ID: 2G8D).Communicated by Ramaswamy H. Sarma.

Optoelectronic and charge transport properties of D-n-A type 1,3,5-triazine derivatives: A combined experimental and DFT study.

The synthesis of five D-n-A type star-shaped octupolar molecules is presented in the current work. The exploration of the potential applicability of molecules under study in organic optoelectronics as electron or hole transporting materials is carried out by DFT methods. All the molecules have a 1,3,5-triazine core, which acts as an electron acceptor (A). Phenyl ring and pyridine ring act as electron donors (D) in AZ and PZ series of molecules respectively. The donor and acceptor core are connected by -NH bridge (n). The crystal structure of a molecule in the PZ series is elucidated. Thermogravimetric studies are carried out to confirm the thermal stability of molecules. The frontier molecular orbitals of molecules are characterized with the help of cyclic voltammetry. With the assistance of DFT methodologies, the whole research presented in this work focuses on the electronic excitations, reorganization energies, electron affinity, ionization potential and features of frontier molecular orbitals of molecules. The investigation of the variation of optoelectronic properties of molecules with changing patterns of nucleophilic substitution on 1,3,5-triazine core and presence of a hetero (nitrogen) atom in the donor part of the molecule is also accomplished.

Structural assessment and identification of 11ß-hydroxysteroid dehydrogenase type 1 inhibitors.

Communicated by Ramaswamy H. Sarma.