Crystal Structure, Spectral investigations, DFT and Antimicrobial activity of Brucinium Benzilate (BBA)

Abstract The unreported Brucinium Benzilate (BBA) crystal and hirshfeld surface analysis indicated the influence of intramolecular hydrogen bonding network. The protonation of tertiary nitrogen occurs as it is most basic. The protonated N-H+ proton was observed at 7.08 ppm and the benzilate carbon COO- at 178.41 ppm. Molecular electrostatic potential (MEP) studies indicated the electron-rich and electron-deficient sites in the molecule for understanding BBA interaction with an enzyme. Frontier molecular orbital (FMO) studies indicated that it is thermodynamically stable and HOMO-LUMO energy gap was found to be 4.454 eV. The highest interaction as the energy (322.86 kcal/mol) between tertiary ammonium N(LP) and H+. The compound showed the inhibition of Bacillus cereus and Salmonella typhimurium bacteria. ADMET properties indicated that BBA has drug characteristics in binding plasma protein.

Download Full-text

Crystal structure and DFT study of a zinc xanthate complex

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019013148 ◽

2019 ◽

Vol 75 (11) ◽

pp. 1582-1585 ◽

Cited By ~ 2

Author(s):

Adnan M. Qadir ◽

Sevgi Kansiz ◽

Necmi Dege ◽

Georgina M. Rosair ◽

Igor O. Fritsky

Keyword(s):

Molecular Structure ◽

Electrostatic Potential ◽

Density Functional ◽

Molecular Electrostatic Potential ◽

Energy Gap ◽

Three Dimensional ◽

Intramolecular Interactions ◽

Lumo Energy ◽

Functional Theory ◽

Homo Lumo

In the title compound, bis(2-methoxyethyl xanthato-κS)(N,N,N′,N′-tetramethylethylenediamine-κ2 N,N′)zinc(II) acetone hemisolvate, [Zn(C4H7O2S2)2(C6H16N2)]·0.5C3H6O, the ZnII ion is coordinated by two N atoms of the N,N,N′,N′-tetramethylethylenediamine ligand and two S atoms from two 2-methoxyethyl xanthate ligands. The amine ligand is disordered over two orientations and was modelled with refined occupancies of 0.538 (6) and 0.462 (6). The molecular structure features two C—H...O and two C—H...S intramolecular interactions. In the crystal, molecules are linked by weak C—H...O and C—H...S hydrogen bonds, forming a three-dimensional supramolecular architecture. The molecular structure was optimized using density functional theory (DFT) at the B3LYP/6–311 G(d,p) level. The smallest HOMO–LUMO energy gap (3.19 eV) indicates the suitability of this crystal for optoelectronic applications. The molecular electrostatic potential (MEP) further identifies the positive, negative and neutral electrostatic potential regions of the molecules. Half a molecule of disordered acetone was removed with the solvent-mask procedure in OLEX2 [Dolomanov et al. (2009). J. Appl. Cryst. 42, 339–341] and this contribition is included in the formula.

Download Full-text

DFT study and NBO analysis of solvation/substituent effects of 3-phenylbenzo[d]thiazole-2(3H)-imine derivatives

Journal of the Serbian Chemical Society ◽

10.2298/jsc200421058m ◽

2020 ◽

Vol 85 (11) ◽

pp. 1445-1462

Author(s):

Marzieh Miar ◽

Abolfazl Shiroudi ◽

Khalil Pourshamsian ◽

Ahmad Oliaey ◽

Farhad Hatamjafari

Keyword(s):

Charge Transfer ◽

Relative Stability ◽

Energy Gap ◽

Substituent Effects ◽

Nbo Analysis ◽

Frontier Molecular Orbital ◽

Thiazole Ring ◽

Chemical Thermodynamics ◽

Lumo Energy ◽

Homo Lumo

In this work, to determine natural bond orbital (NBO) analysis, solvation and substituent effects for electron-releasing substituents (CH3, OH) and electron-withdrawing derivatives (Cl, NO2, CF3) in para positions on the molecular structure of the synthesized 3-phenylbenzo[d]thiazole-2(3H)-imine derivatives 1?6 (H (1), CH3 (2), Cl (3), OH (4), CF3 (5), NO2 (6)) in the selected solvents (acetone, toluene, and ethanol) and gas-phase employing polarizable continuum method (PCM) model were studied at the M06-2x/6- -311++G(d,p) level of theory. The relative stability of the studied compounds was affected by the possibility of intramolecular interactions between substituents and the electron donor/acceptor centers of the thiazole ring. Furthermore, atomic charges electron density, chemical thermodynamics, energetic properties, dipole moments, and the nucleus-independent chemical shifts (NICS) of the studied compounds and their relative stability are considered. The dipole moment values and the HOMO?LUMO energy gap reveal the different charge transfer possibilities within the considered molecules. Frontier molecular orbital (FMO) analysis revealed that compound 6 has very small HOMO-LUMO energy gaps in the considered phases, and thus is kinetically less stable. The obtained HOMO-LUMO energy gap corresponds to intramolecular hyperconjugative interactions ?? ?*. Finally, NBO analysis is carried out to demonstrate the charge transfer between localized bonds and lone pairs.

Download Full-text

A p–n fusion strategy to design bipolar organic materials for high-energy-density symmetric batteries

Journal of Materials Chemistry A ◽

10.1039/d1ta02059e ◽

2021 ◽

Author(s):

Jihyeon Kim ◽

Heechan Kim ◽

Sechan Lee ◽

Giyun Kwon ◽

Taewon Kang ◽

...

Keyword(s):

Energy Density ◽

Organic Material ◽

Energy Gap ◽

High Energy ◽

High Energy Density ◽

Lumo Energy ◽

Fusion Strategy ◽

Redox Active ◽

Bipolar Type ◽

Homo Lumo

A new bipolar-type redox-active organic material with a wide HOMO–LUMO energy gap is designed though the ‘p–n fusion’ strategy.

Download Full-text

STRUCTURES, ABSORPTION SPECTRA, AND ELECTRONIC PROPERTIES OF POLYFLUORENE AND ITS DERIVATIVES: A THEORETICAL STUDY

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633606002520 ◽

2006 ◽

Vol 05 (03) ◽

pp. 595-608 ◽

Cited By ~ 13

Author(s):

KRIENGSAK SRIWICHITKAMOL ◽

SONGWUT SURAMITR ◽

POTJAMAN POOLMEE ◽

SUPA HANNONGBUA

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Energy Gap ◽

Level Energy ◽

Excitation Energies ◽

Lumo Energy ◽

Functional Theory ◽

Local Energy Minimum ◽

Pi Systems ◽

Homo Lumo

The structural and energetic properties of polyfluorene and its derivatives were investigated, using quantum chemical calculations. Conformational analysis of bifluorene was performed by using ab initio (HF/6-31G* and MP2/6-31G*) and density functional theory (B3LYP/6-31G*) calculations. The results showed that the local energy minimum of bifluorene lies between the coplanar and perpendicular conformation, and the B3LYP/6-31G* calculations led to the overestimation of the stability of the planar pi systems. The HOMO-LUMO energy differences of fluorene oligomers and its derivatives — 9,9-dihexylfluorene (DHPF), 9,9-dioctylfluorene (PFO), and bis(2-ethylhexyl)fluorene (BEHPF) — were calculated at the B3LYP/6-31G* level. Energy gaps and effective conjugation lengths of the corresponding polymers were obtained by extrapolating HOMO-LUMO energy differences and the lowest excitation energies to infinite chain length. The lowest excitation energies and the maximum absorption wavelength of polyfluorene were also performed, employing the time-dependent density functional theory (TDDFT) and ZINDO methods. The extrapolations, based on TDDFT and ZINDO calculations, agree well with experimental results. These theoretical methods can be useful for the design of new polymeric structures with a reducing energy gap.

Download Full-text

Theoretical investigation on tautomerism and NLO properties of Salicylideneaniline derivatives

Canadian Journal of Physics ◽

10.1139/cjp-2021-0175 ◽

2021 ◽

Author(s):

N. Daho ◽

N. Benhalima ◽

F. KHELFAOUI ◽

O. SADOUKI ◽

M. Elkeurti ◽

...

Keyword(s):

Optical Properties ◽

Density Functional ◽

Energy Gap ◽

Intramolecular Proton Transfer ◽

Basis Set ◽

Frontier Molecular Orbital ◽

Molecular Orbital Calculations ◽

Visible Absorption ◽

Charge Delocalization ◽

Intramolecular Hydrogen

In this work, a comprehensive investigation of the salicylideneaniline derivatives is carried out using density functional theory to determine their linear and non-linear optical properties. Geometry optimizations, for gas and solvent phases, of the tautomers (enol and keto forms) are calculated using B3LYP levels with 6–31G (d,p) basis set . An intramolecular proton transfer, for 1SA-E and 2SA-E, is performed by a PES scan process at the B3LYP/6-31G (d,p) level. The optical properties are determined and show that they have extremely high nonlinear optical properties. In addition, the RDG analysis, MEP, and gap energy are calculated. The low energy gap value indicates the possibility of intramolecular charge transfer. The frontier molecular orbital calculations clearly show the inverse relationship of HOMO–LUMO gap with the first-order hyperpolarizability (β = 59.6471 × 10-30 esu), confirming that the salicylideneaniline derivatives can be used as attractive future NLO materials. Therefore, the reactive sites are predicted using MEP and the visible absorption maxima are analyzed using a theoretical UV–Vis spectrum. Natural bond orbitals are used to investigate the stability, charge delocalization, and intramolecular hydrogen bond.

Download Full-text

5-Methyl-1,3-phenylene bis[5-(dimethylamino)naphthalene-1-sulfonate]: crystal structure and DFT calculations

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019009058 ◽

2019 ◽

Vol 75 (7) ◽

pp. 1079-1083

Author(s):

Tanwawan Duangthongyou ◽

Ramida Rattanakam ◽

Kittipong Chainok ◽

Songwut Suramitr ◽

Thawatchai Tuntulani ◽

...

Keyword(s):

Dft Calculations ◽

Energy Gap ◽

Rotation Axis ◽

Three Dimensional ◽

Hydrogen Atoms ◽

Lumo Energy ◽

Compound C ◽

Dansyl Group ◽

Weak Hydrogen Bonds ◽

Homo Lumo

The title compound, C31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methylphenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO–LUMO energy gap was found to be 2.99 eV and indicates n→π* and π→π* transitions within the molecule.

Download Full-text

SOLVENT EFFECTS ON THE ELECTRONIC STRUCTURE AND NON-LINEAR OPTICAL PROPERTIES OF PYRENE AND SOME OF ITS DERIVATIVES BASED ON DENSITY FUNCTIONAL THEORY

FUDMA Journal of Sciences ◽

10.33003/fjs-2020-0404-477 ◽

2021 ◽

Vol 4 (4) ◽

pp. 236-251

Author(s):

A. S. Gidado ◽

L. S. Taura ◽

A. Musa

Keyword(s):

Density Functional Theory ◽

Gas Phase ◽

Density Functional ◽

Energy Gap ◽

Chemical Reactivity ◽

Basis Set ◽

Lumo Energy ◽

Functional Theory ◽

Organic Optoelectronic ◽

Homo Lumo

Pyrene (C16H10) is an organic semiconductor which has wide applications in the field of organic electronics suitable for the development of organic light emitting diodes (OLED) and organic photovoltaic cells (OPV). In this work, Density Functional Theory (DFT) using Becke’s three and Lee Yang Parr (B3LYP) functional with basis set 6-311++G(d, p) implemented in Gaussian 03 package was used to compute total energy, bond parameters, HOMO-LUMO energy gap, electron affinity, ionization potential, chemical reactivity descriptors, dipole moment, isotropic polarizability (α), anisotropy of polarizability ( Δ∝) total first order hyper-polarizability () and second order hyperpolarizability (). The molecules used are pyrene, 1-chloropyrene and 4-chloropyrene in gas phase and in five different solvents: benzene, chloroform, acetone, DMSO and water. The results obtained show that solvents and chlorination actually influenced the properties of the molecules. The isolated pyrene in acetone has the largest value of HOMO-LUMO energy gap of and is a bit closer to a previously reported experimental value of and hence is the most stable. Thus, the pyrene molecule has more kinetic stability and can be described as low reactive molecule. The calculated dipole moments are in the order of 4-chloropyrene (1.7645 D) < 1-chloropyrene (1.9663 D) in gas phase. The anisotropy of polarizability ( for pyrene and its derivatives were found to increase with increasing polarity of the solvents. In a nutshell, the molecules will be promising for organic optoelectronic devices based on their computed properties as reported by this work.

Download Full-text

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

The Journal of Organic Chemistry ◽

10.1021/acs.joc.0c02343 ◽

2020 ◽

Vol 86 (1) ◽

pp. 770-781

Author(s):

Akihiro Shimizu ◽

Yu Ishizaki ◽

Shun Horiuchi ◽

Takashi Hirose ◽

Kenji Matsuda ◽

...

Keyword(s):

Energy Gap ◽

Lumo Energy ◽

Homo Lumo

Download Full-text

Strategic design of thiophene-fused nickel dithiolene derivatives for efficient NLO response

Physical Chemistry Chemical Physics ◽

10.1039/c8cp01592a ◽

2018 ◽

Vol 20 (28) ◽

pp. 19007-19016 ◽

Cited By ~ 3

Author(s):

Manoj Majumder ◽

Anirban Misra

Keyword(s):

Energy Gap ◽

First Hyperpolarizability ◽

Lumo Energy ◽

Strategic Design ◽

Nlo Response ◽

Acceptor Group ◽

Donor Acceptor ◽

Homo Lumo

The zwitterionic donor–acceptor group significantly reduces the HOMO–LUMO energy gap resulting in an enormous increase in the first hyperpolarizability values.

Download Full-text