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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]

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]

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]

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]

• 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]