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

Abstract

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 is thus 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.

Designing dibenzosilole core based, A2–π–A1–π–D–π–A1–π–A2type donor molecules for promising photovoltaic parameters in organic photovoltaic cells

“…Usually, the greater the capability of an electron withdrawing group to extract the electrons from the donor region, the decreased will be value of the HOMO and LUMO energies. 46 The band-gap, between the energy values of the FMOs, is closely related to the absorption maxima, as molecules with a lower band-gap tend to have a higher value of this important parameter. In addition, a lower band-gap increases the reactivity and also the charge transfer within the molecule.…”

Thiohydantoins as Potential Antioxidant Agents: In vitro and in silico evaluation

“…The energies of frontier molecular orbitals, HOMO (E HOMO , highest occupied molecular orbital) and LUMO (E LUMO , lowest unoccupied molecular orbital) energies indicate the tendency of a molecule donate and accepted electrons, respectively [26] . In addition, a small difference between energies of these orbitals (gap HOMO‐LUMO =E LUMO ‐ E HOMO ) indicate a high chemical reactivity and low kinetic stability of the molecule [27] …”

L‐Proline Catalyzed Synthesis of Steroidal Pyridones And Their DFT Studies

“…Frontier molecular orbital (HOMO and LUMO) analysis is widely used to define the electronic properties of the molecules. [40] The HOMO, LUMO energies, and HOMO-LUMO gap of the molecule are widely employed to know about the various chemical reactivity descriptors of the molecule. The high and low reactivity (or low and high kinetic stability) of the molecule is explained by small and large gaps respectively.…”