Evaluation of the excited state dynamics, photophysical properties, and the influence of donor substitution in a donor-$$\pi$$-acceptor system

Louis, Hitler; Ifediora, Linda P.; Enudi, Obieze C.; Unimuke, Tomsmith O.; Asogwa, Fredrick C.; Moshood, Yusuff L.

doi:10.1007/s00894-021-04875-1

Cited by 39 publications

(13 citation statements)

References 55 publications

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“…Chemical hardness is perceived as the capacity to resist electron density transfer with surrounding species. 40 − 42 Thus, CHP and FCHP are termed species with less propensity to exchange electron density with the immediate electronic environment by their high global hardness and low global softness values; this also shows that these species will likely be more reactive toward hard bases and generally more reactive. Thiepane has the highest softness and lowest hardness value and as such is the least reactive of the studied compounds toward soft bases based on Pearson’s hard–soft acid–base theory.…”

Section: Results and Discussionmentioning

confidence: 99%

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

et al. 2022

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The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered.

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Section: Results and Discussionmentioning

confidence: 99%

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

et al. 2022

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“…Potential energy distribution (PED) analysis was performed to achieve the FT-IR absorption parameters [38][39]. Other electronic property determinations like natural bonding orbital (NBO) analysis [40] and vertical excitation analysis of the first 5 excitations of FTPF are also pivotal in this study, so as to register the important intra-monomer, hence polymeric electronic transitions of our titled molecule [21][22][23]. The electronic excitations and oscillator strength parameters obtained from the UV-vis calculations were employed for the investigation of the photovoltaic properties.…”

Section: )mentioning

confidence: 99%

“…Excitations are classified as charge transfer (CT), Rydberg or local excitations (LE) depending on the spatial distribution, overlapping extent, centroid position, etc. which are deduced from the various indices considered in this work [23]. Calculations for the various indices in this excitation study were done using equations from Le Bahers et al ( 2011) [48].…”

Section: Computational Detailsmentioning

confidence: 99%

“…FMO analysis is an important approach to the study of potential materials for electronic applications, it does not only expose the energies of molecular orbitals, but also explain the distributions of these orbitals around the molecular system [22,23]. For an appreciable knowledge on the electronic excitation properties of FTPF, the HOMO-2, HOMO-1, HOMO, LUMO, LUMO+1 and LUMO+2…”

Section: Frontier Molecular Orbital (Fmo) Analysismentioning

confidence: 99%

“…The D-A-D systems are classified by high conjugated bonding systems which allow strong electronic transitions. Dyes are other category of organic materials applied in photovoltaics, due to their high π-electron conjugations, leading to great electronic excitations and transitions [21][22][23]. These systems are characterized with low HOMO/LUMO energy gap, which gives insight into why these molecules act as semiconductors [24].…”

Section: Introductionmentioning

confidence: 99%

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Understanding the Electronic Interactions, Vertical Excitation Analysis, and the Photovoltaic Properties of 5-(2-ethylhexyl)-1,3-di(furan-2-yl)-4H-thieno[3,4-c]pyrrole-4,6-dione

Enudi

Louis

Ogunwale

et al. 2021

Preprint

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Organic photovoltaic (OPV) are a promising new class of photovoltaic as they offer several advantageous features including large surface area to volume ratio, low cost, lightweight properties, and durability. The limitation of OPV that prevented their adoption for use in the past was their low power conversion efficiency (PCE) but that drawback has been solved by the development of the donor-acceptor-donor (D-A-D) system with high conversion efficiencies. Herein, 5-(2-ethylhexyl)-1,3-di (furan-2-yl)-4H-thieno [3,4-c]pyrrole-4,6(5H)-dione (FTPF), a donor-acceptor-donor monomer was investigated for its optoelectronic, excited state, and photovoltaic properties using a density functional theory (DFT) and time-dependent density function theory (TD-DFT) at the B3LYP/6-31+G(d,p) theoretical method. The spectral analysis (FT-IR, UV-vis, and NMR), electronic molecular properties, natural bonding orbitals (MOs and NBOs) analyses, and excitation were studied at this level in gas, hexane, DMF, and THF. The UV-Vis spectrum showed that FTPF exhibited mono-absorption in non-polar gas and hexane, but dual absorptions in polar solvents (DMF and THF) having maximum wavelength (λmax) at 351, 359, 371 and 373 nm in gas, hexane, THF, and DMF respectively, showing a major red shift as solvent became polar. The hole-electron excitation studies of the first five singlet states: S0→S1/S2/S3/S4/S5 in gas and DMF phases showed that S0→S1 is a delocalized π→π* Rydberg excitations originating from the D-A-D C=C π bonds, S0→S2 is π→π* local excitation, while S0→S3 in water occurred as an n→π* from the carbonyl and azolide groups of the acceptor unit, but n→π* charge transfer (CT) in DMF. The S0→S5 in water and S0→S4 are n→π* LE type excitations, while S0→S5 in DMF conformed to a delocalized π→π* excitation extended over the D-A-D conjugated backbone. FTPF provided efficient electron injection in all studied solvent; showing that FTPF is a sure-bet for opto-electronic application.

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Experimental and theoretical studies of the influence of alkyl groups on the photovoltaic properties of (E)-6-((2, 3-dihydroxylnaphthalene)diazenyl)-1H-benzoisoquinoline-1,3-dione-based organic solar cell

et al. 2022

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Evaluation of the excited state dynamics, photophysical properties, and the influence of donor substitution in a donor-$$\pi$$-acceptor system

Cited by 39 publications

References 55 publications

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

Understanding the Electronic Interactions, Vertical Excitation Analysis, and the Photovoltaic Properties of 5-(2-ethylhexyl)-1,3-di(furan-2-yl)-4H-thieno[3,4-c]pyrrole-4,6-dione

Experimental and theoretical studies of the influence of alkyl groups on the photovoltaic properties of (E)-6-((2, 3-dihydroxylnaphthalene)diazenyl)-1H-benzoisoquinoline-1,3-dione-based organic solar cell

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