Aromaticity indices, electronic structural properties, and fuzzy atomic space investigations of naphthalene and its aza-derivatives

Edim, Moses M.; Enudi, Obieze C.; Asuquo, Bassey B.; Louis, Hitler; Bisong, Emmanuel A.; Agwupuye, John A.; Apebende, Chioma G.; Odey, Joseph O.; Joseph, Innocent; Bassey, Francisca I.

doi:10.1016/j.heliyon.2021.e06138

Cited by 44 publications

(20 citation statements)

References 35 publications

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“…From Fig. 4, Eg is 2.95 eV, which is relatively low [27][28][29][30][31][32], hence excitation from the HOMO to LUMO is easily feasible; this is a basic property of a reactive molecule. Also, the energy gap between HOMO-1 and LUMO + 1 orbitals was determined for a more explicit information about the studied molecule; we obtained Eg to be 4.94 eV.…”

Section: Frontier Molecular Orbital (Fmo) Analysismentioning

confidence: 97%

“…Also, the locations and distributions of these orbitals (HOMO-1, HOMO, LUMO and LUMO + 1) were determined abreast the pictorial representations in Fig. 4, in order to understand the orbital properties of the valence orbitals [28]. The highest occupied molecular orbital (HOMO) is concentrated around C18, and it is basically from a p-type orbital on C18 (18.69%).…”

Section: Frontier Molecular Orbital (Fmo) Analysismentioning

confidence: 99%

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Synthesis, characterization, DFT, and TD-DFT studies of (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite)

et al. 2021

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In this study, (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite), a cyanurated H-acid (CHA) azo dye, was synthesized and characterized using FT-IR spectrophotometer and GC-MS spectroscopy. A density functional theory (DFT) based B3LYP and CAM-B3LYP method with 6–311 + G (d,p) basis set analysis was computed for HOMO-LUMO, natural bonding orbitals (NBO), UV-Vis absorptions and excitation interactions, in order to understand its molecular orbital excitation properties. A low Energy gap (Eg) of 2.947 eV was obtained from the molecular orbital analysis, which showed that HOMO to LUMO transition is highly feasible; hence CHA is adequate for diverse electronic and optic applications. Studies of the first five excitations (S0 → S1/S2/S3/S4/S5) of CHA revealed that S0 → S1 and S0 → S3 are π → π* type local excitations distributed around the –N=N– group; S0 → S2, a Rydberg type local excitation; S0 → S4, a highly localized π → π* excitation; while S0 → S5 is an n → π* charge transfer from a benzene ring to –N=N– group. From NBO analysis, we obtained the various donor–acceptor orbital interactions contributing to the stabilization of the studied compound. Most significantly, some strong hyper-conjugations (n → n*) within fragments, and non-bondingand anti-bonding intermolecular (n → n*/π* and π → n*/π*) interactions were observed to contribute appreciable energies. This study is valuable for understanding the molecular properties of the azo dyes compounds and for synthesizing new ones in the future.

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Section: Frontier Molecular Orbital (Fmo) Analysismentioning

confidence: 97%

Section: Frontier Molecular Orbital (Fmo) Analysismentioning

confidence: 99%

Synthesis, characterization, DFT, and TD-DFT studies of (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite)

et al. 2021

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“…The enthalpies and Gibbs free energies of formation of the various titled clusters were obtained using Eqs. (11), (12), and (13). Where calculations were performed at STP (T ¼ 298K; P ¼ 1 atm)…”

Section: Bementioning

confidence: 99%

“…Eqs. (8), ( 9), (10), (11), (12), and (13) was adopted from the reports from Ochterski in 2000 [52,53].…”

Section: Bementioning

confidence: 99%

“…All thermodynamic calculations are done at 298.15K and 1atm, considering one mole of complex, by applying Eqs. (8), ( 9), ( 10), ( 11), (12), and (13). The thermodynamics parameters of all studied fragments were calculated with DFT/B3LYP method at 631-G (d) basis, the ΔH f of water at STP is calculated to be -76.384 eV at this level.…”

Section: Thermodynamics Considerationsmentioning

confidence: 99%

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Understanding the aqueous chemistry of quinoline and the diazanaphthalenes: insight from DFT study

Enudi

Louis

Edim

et al. 2021

Heliyon

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The inter-fragment interactions at various binding sites and the overall cluster stability of quinolone (QNOL), cinnoline (CNOL), quinazoline (QNAZ), and quinoxaline (QNOX) complexes with H 2 O were studied using the density functional theory (DFT) approach. The adsorption and H-bond binding energies, and the energy decomposition mechanism was considered to determine the relative stabilization status of the studied clusters. Scanning tunneling microscopy (STM), natural bonding orbitals (NBO) and charge decomposition were studied to expose the electronic distribution and interaction between fragments. The feasibility of formations of the various complexes were also studied by considering their thermodynamic properties. Results from adsorption studies confirmed the actual adsorption of H 2 O molecules on the various binding sites studied, with QNOX clusters exhibiting the best adsorptions. Charge decomposition analysis (CDA) revealed significant charge transfer from substrate to H 2 O fragment in most complexes, except in QNOL, CNOL and QNAZ clusters with H 2 O at binding position 4, where much charges are back-donated to substrate. The O-H inter-fragment bonds was discovered to be stronger than counterpart N-H bonds in the complexes, whilst polarity indices confirmed N-H as more polar covalent than O-H bonds. Thermodynamic considerations revealed that the formation process of all studied complexes are endothermic (þve ΔH f ) and non-spontaneous (þve ΔG f ).

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Tricyclic 1,4‐Diphosphinines: Local vs. Global Aromaticity

Kalisch,

Brehm,

Streubel

2024

ChemPhysChem

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Abstract1D and 2D (Sigma only model) calculations were performed on recently established tricyclic 1,4‐diphosphinines as well as related benzene and pyrazine derivatives. The study was extended to evaluate the effect of the fused rings on the overall aromatic properties with a special focus on functional groups such as carbenes. The effect of non‐aromatic heterocycles on the local ring current of the central ring is small, while aromatic heterocycles (e. g. NHC, imidazolium) lead to a global aromaticity. A higher sulfur content of the adjacent five‐membered rings reduces the central ring current. The comparison to related tricyclic benzene and pyrazine derivatives showed that the 1,4‐diphosphinine systems resemble more closely the situation in the benzene derivatives than the pyrazines. The effect of charged systems was studied using bis(TTF)‐fused 1,4‐diphosphinines and, according to values, the neutral form doesn't possess significant aromaticity but the tetracation resembles the global aromatic situation observed for other heterocycles in this study.

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Aromaticity indices, electronic structural properties, and fuzzy atomic space investigations of naphthalene and its aza-derivatives

Abstract: The aromaticity and CDFT properties of naphthalene and its aza-derivatives were theoretically investigated using density functional theory (DFT) electronic structure method. The reactivity and chemistry

Cited by 44 publications

References 35 publications

Synthesis, characterization, DFT, and TD-DFT studies of (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite)

Synthesis, characterization, DFT, and TD-DFT studies of (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite)

Understanding the aqueous chemistry of quinoline and the diazanaphthalenes: insight from DFT study

Tricyclic 1,4‐Diphosphinines: Local vs. Global Aromaticity

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