Density Functional Theory Computational Studies Research Articles

A Computational DFT Study of the Stereoinversion of Succinimide Residues Formed in Proteins and Peptides Catalyzed by a Hydrogen Phosphate Ion: An Unsymmetrical SE1 Mechanism

Succinimide residues formed spontaneously from aspartic acid (Asp) and asparagine (Asn) residues in proteins and peptides are stereochemically unstable, undergoing partial l-to-d stereoinversion, and this is responsible for the d-Asp and d-β-Asp residues found in long-lived proteins. These stereoinverted abnormal amino acid residues are believed to be related to aging and some age-related diseases such as cataracts. Although the succinimide stereoinversion is nonenzymatic, a catalyst is required for it to occur at physiological temperature. In this study, it was found by density functional theory (DFT) calculations that a hydrogen phosphate ion (HPO42−) can effectively catalyze the stereoinversion of the succinimide intermediate. The HPO42− ion abstracts a proton from the asymmetric carbon atom of the succinimide residue to form an enolate intermediate. Then, while the resultant dihydrogen phosphate ion (H2PO4−) remains bound to the enolate ion, a water molecule donates a proton to the enolate intermediate on the opposite side from the phosphate (which is the rate-determining step) to produce the inverted carbon atom. The calculated activation barrier (ca. 90 kJ mol−1) is consistent with a slow in vivo reaction. The present found mechanism can be termed the “unsymmetrical SE1” or “pseudo-SE2” mechanism.

Electrochemicaland computational insightsinto the utilization of an N-heteroaromatic containing compound2-(4-Methoxy-phenyl)-5-naphthalen-2-yl-[1,3,4]oxadiazole as a promising anticorrosive agent for mild steel in corrosive medium

In this investigation, the corrosion inhibition properties of an N-heteroaromatic containing compound 2-(4-Methoxy-phenyl)-5-naphthalen-2-yl-[1,3,4]oxadiazole (MPNO), against mild steel (MS) in 1 M HCl using various analytical techniques have been examined. This study included weight-loss measurements at different temperatures (303–323 K), electrochemical analyses using Electrochemical Impedance Spectroscopy (EIS) and Potentiodynamic Polarization (PDP), and surface morphology investigations with Scanning Electron Microscopy (SEM). The experimental results demonstrated that MPNO exhibited excellent corrosion inhibition efficiency of 85.53% at a minimal 400 ppm inhibitor concentration with a mixed-type inhibition mechanism, as evidenced by the charge transfer resistance (RCT) value of 327.02 Ω.cm2 derived from the EIS analysis. Additionally, the analysis of quantum chemical descriptors revealed EHOMO (−8.6335 eV), ELUMO (−1.0277 eV), energy gap (ΔE = 7.60 eV), dipole moment (µ = 2.618 D), indicating inhibitor capability to acquire electrons and donate them to the metal's vacant d-orbitals, thus enhancing its adsorption activity and inhibitory properties. The density functional theory (DFT) computational studies complemented the experimental findings and provided a deeper understanding of the interaction modes between the inhibitors and the MS surface.

An Acid-Responsive Fluorescent Molecule for Erasable Anti-Counterfeiting.

A tetraphenylethylene (TPE) derivative, TPEPhDAT, modified by diaminotriazine (DAT), was prepared by successive Suzuki-Miyaura coupling and ring-closing reactions. This compound exhibits aggregation-induced emission enhancement (AIEE) properties in the DMSO/MeOH system, with a fluorescence emission intensity in the aggregated state that is 5-fold higher than that of its counterpart in a dilute solution. Moreover, the DAT structure of the molecule is a good acceptor of protons; thus, the TPEPhDAT molecule exhibits acid-responsive fluorescence. TPEPhDAT was protonated by trifluoroacetic acid (TFA), leading to fluorescence quenching, which was reversibly restored by treatment with ammonia (on-off switch). Time-dependent density functional theory (TDDFT) computational studies have shown that protonation enhances the electron-withdrawing capacity of the triazine nucleus and reduces the bandgap. The protonated TPEPhDAT conformation became more distorted, and the fluorescence lifetime was attenuated, which may have produced a twisted intramolecular charge transfer (TICT) effect, leading to fluorescence redshift and quenching. MeOH can easily remove the protonated TPEPhDAT, and this acid-induced discoloration and erasable property can be applied in anti-counterfeiting.

Multiple pathways for lanthanide sensitization in self-assembled aqueous complexes

Lanthanide photoluminescence (PL) emission has attracted much attention for technological and bioimaging applications because of its particularly interesting features, such as narrow emission bands and very long PL lifetimes. However, this emission process necessitates a preceding step of energy transfer from suitable antennas. While biocompatible applications require luminophores that are stable in aqueous media, most lanthanide-based emitters are quenched by water molecules. Previously, we described a small luminophore, 8-methoxy-2-oxo-1,2,4,5-tetrahydrocyclopenta[de]quinoline-3-phosphonic acid (PAnt), which is capable of dynamically coordinating with Tb(III) and Eu(III), and its exchangeable behavior improved their performance in PL lifetime imaging microscopy (PLIM) compared with conventional lanthanide cryptate imaging agents. Herein, we report an in-depth photophysical and time-dependent density functional theory (TD–DFT) computational study that reveals different sensitization mechanisms for Eu(III) and Tb(III) in stable complexes formed in water. Understanding this unique behavior in aqueous media enables the exploration of different applications in bioimaging or novel emitting materials.

A computational DFT study of Imidazolium based Ionic liquids: binding energy calculation with different anions using Solvation Model

Basic knowledge of chemical events in the gaseous or liquid phase, as well as on surfaces, is required to determine the macroscopic process. The structure of ionic liquids were investigated using quantum chemistry. Cation and anion can bond together, according to the findings. Their binding and interaction energies reveal that they are produced by hydrogen bonds. The mechanism of a room temperature ionic liquid, such as [BMIM][Cl] (1-butyl-3-Methylimidazolium chloride) monomer, was studied using Density functional theory (DFT) computations using the modern continum solvation model (IEFPCM-SMD). Ionic liquid [IL] contains both anions and cations, allowing for greater intermolecular interactions. By analyzing the relative minimum energy of [BMIM][Cl] in the presence and absence of water, we were able to establish the minimum energy structures and probable Cl anion binding sites in [BMIM][Cl] ionic liquid. We have found that all 1-butyl-3-methylimidazolium halide ILs investigated had trans conformations due to the butyl group’s dihedral angles. GUB JOURNAL OF SCIENCE AND ENGINEERING, Vol 9(1), 2022 P 66-70

Superelectrophilic Nonclassical Carbocations.

The chemistry of dicationic and tricationic 2-norbornyl cations has been studied. A series of N-heterocyclic functionalized norborneol substrates were prepared and ionization of these compounds in superacid provided superelectrophilic species. These highly charged 2-norbornyl cations were found to react with arene nucleophiles in high yields and stereoselectivity. Density functional theory computational studies suggest that increasing positive charge on the structures tends to enhance the degree of nonclassical (or 3-center-2-electron) bonding through separation of the cationic charges.

Multifunctional anti-Alzheimer's agents: Synthesis, biological evaluation, and molecular docking study of new 2-phenoxyacetamide/3-phenoxypropanamide/4-oxobutanamide derivatives

In the current study, three series of new compounds were designed and synthesized through hit optimization, based on the hit compound with a structure (E)-N-(4-{[benzyl(methyl)amino]methyl}thiazol-2-yl)-3-(3,4-dimethoxyphenyl)prop‑2-enamide, which was found as a potential multifunctional anti-Alzheimer agent in our previous study. Then, the biological activities of synthesized compounds (4a-c, 13a-b and 15a-c) were evaluated. The results indicated that 4b, a 2-phenoxyacetamide derivative, exhibited good multifunctional activities. Namely, compound 4b displayed better BChE inhibition (BChE IC50 = 2.10 µM) and antioxidant activity (ORAC = 1.18 Trolox equivalents) compared to the hit compound (BChE IC50 = 14.70 µM, ORAC = 0.5 Trolox equivalents). Additionally, 4b was able to chelate all tested biometals and it also exhibited a neuroprotective effect (63 %), comparable to reference ferulic acid (77 %) while maintaining its safety upon PC12 cell line. When it comes to lowering the levels of TNF-α, NO, IL-1β, and IL-6, 4b performed better activity, relative to the other synthesized compounds. Subsequently, in silico studies such as physicochemical properties, density functional theory (DFT) computational approach and molecular docking studies were performed.

Reactivity of a Hexaaryldiboron(6) Dianion as Boryl Radical Anions.

Our study unveils a novel approach to accessing boryl radicals through the spontaneous homolytic cleavage of B-B bonds. We synthesized a hexaaryl-substituted diboron(6) dianion, 1, via the reductive B-B coupling of 9-borafluorene. Intriguingly, compound 1 exhibits the ability to undergo homolytic B-B bond cleavage, leading to the formation of boryl radical anions, as confirmed by EPR studies, in the presence of the 2.2.2-cryptand at room temperature. Moreover, it directly reacts with diphenylacetylene, producing an unprecedented 1,6-diborylated allene species, where the phenyl ring is dearomatized. Density functional theory computational studies suggest that homolytic B-B bond cleavage is favored in the reaction path, and the formation of the boryl radical anion is crucial for dearomatization. Additionally, it achieves the dearomative diborylation of anthracene and the activation of elemental sulfur/selenium under mild conditions. The borylation products have been successfully characterized by NMR spectra, HRMS, and X-ray single-crystal diffraction.

Enhanced Activity and Selectivity for Nitrogen Reduction Reaction in Electrode-based Heterostructures: A DFT Computational Study.

Developing sustainable and efficient catalysts for ammonia synthesis from atmospheric molecular N2 under ambient conditions presents a significant 21st-century challenge. Two-dimensional heterostructures, particularly single-atom catalysts (SACs) supported on two-dimensional materials, have emerged as a promising avenue due to their remarkable catalytic activity and selectivity. Electrides, characterized by an abundance of free electrons and high surface activity, have attracted substantial attention in this context. Through density functional theory (DFT) calculations, this study proposes electride-graphene heterostructures (EGHS) as catalysts to effectively regulate charge distribution at the catalytic center, facilitating the optimization of catalytic performance. The EGHS model addresses challenges related to excessive adsorbate binding, mitigating electron transfer compared to electride monolayer adsorption. This novel approach utilizes heterogeneous heterostructures to finely tune the catalytic site, optimizing electron input for enhanced catalysis.Based on the optimized charge transfer for N2 activation, the Cr-doped EGHS (Cr@EGHS) exhibits a promising performance in the nitrogen reduction reaction, leading to, a relatively low limiting potential of -0.85 V and high selectivity. The hypothesis charge transfer depend on N2 activation is further supported by modulating the distance between component layers of heterostructure. These findings contribute to design principles for 2D heterostructure catalysts and offer a reference for experimental synthesis.

Electro/Ni Dual-Catalyzed Decarboxylative C(sp3)-C(sp2) Cross-Coupling Reactions of Carboxylates and Aryl Bromide.

Paired redox-neutral electrolysis offers an attractive green platform for organic synthesis by avoiding sacrificial oxidants and reductants. Carboxylates are non-toxic, stable, inexpensive, and widely available, making them ideal nucleophiles for C-C cross-coupling reactions. Here, we report the electro/Ni dual-catalyzed redox-neutral decarboxylative C(sp3)-C(sp2) cross-coupling reactions of pristine carboxylates with aryl bromides. At a cathode, a NiII(Ar)(Br) intermediate is formed through the activation of Ar-Br bond by a NiI-bipyridine catalyst and subsequent reduction. At an anode, the carboxylates, including amino acid, benzyl carboxylic acid, and 2-phenoxy propionic acid, undergo oxidative decarboxylation to form carbon-based free radicals. The combination of NiII(Ar)(Br) intermediate and carbon radical results in the formation of C(sp3)-C(sp2) cross-coupling products. The adaptation of this electrosynthesis method to flow synthesis and valuable molecule synthesis was demonstrated. The reaction mechanism was systematically studied through electrochemical voltammetry and density functional theory (DFT) computational studies. The relationships between the electrochemical properties of carboxylates and the reaction selectivity were revealed. The electro/Ni dual-catalyzed cross-coupling reactions described herein expand the chemical space of paired electrochemical C(sp3)-C(sp2) cross-coupling and represent a promising method for the construction of the C(sp3)-C(sp2) bonds because of the ubiquitous carboxylate nucleophiles and the innate scalability and flexibility of electrochemical flow-synthesis technology.

Electro/Ni Dual‐Catalyzed Decarboxylative C(sp3)−C(sp2) Cross‐Coupling Reactions of Carboxylates and Aryl Bromide

AbstractPaired redox‐neutral electrolysis offers an attractive green platform for organic synthesis by avoiding sacrificial oxidants and reductants. Carboxylates are non‐toxic, stable, inexpensive, and widely available, making them ideal nucleophiles for C−C cross‐coupling reactions. Here, we report the electro/Ni dual‐catalyzed redox‐neutral decarboxylative C(sp3)−C(sp2) cross‐coupling reactions of pristine carboxylates with aryl bromides. At a cathode, a NiII(Ar)(Br) intermediate is formed through the activation of Ar−Br bond by a NiI‐bipyridine catalyst and subsequent reduction. At an anode, the carboxylates, including amino acid, benzyl carboxylic acid, and 2‐phenoxy propionic acid, undergo oxidative decarboxylation to form carbon‐based free radicals. The combination of NiII(Ar)(Br) intermediate and carbon radical results in the formation of C(sp3)−C(sp2) cross‐coupling products. The adaptation of this electrosynthesis method to flow synthesis and valuable molecule synthesis was demonstrated. The reaction mechanism was systematically studied through electrochemical voltammetry and density functional theory (DFT) computational studies. The relationships between the electrochemical properties of carboxylates and the reaction selectivity were revealed. The electro/Ni dual‐catalyzed cross‐coupling reactions described herein expand the chemical space of paired electrochemical C(sp3)−C(sp2) cross‐coupling and represent a promising method for the construction of the C(sp3)−C(sp2) bonds because of the ubiquitous carboxylate nucleophiles and the innate scalability and flexibility of electrochemical flow‐synthesis technology.

Leveraging Nonstrained C-C Bonds for Selective Carboacylation of an Unactivated Alkyne via Transient Dearomatization.

Carboacylation of an unsaturated bond represents a powerful transformation. However, only a few examples of carboacylation of alkyne have been reported through C-C bond scission and reconnection. Here, we report a method of carboacylation of an unactivated alkyne by utilizing nonstrained C-C bonds under gold(I) catalysis. The density functional theory computational and experimental studies reveal that the reaction proceeds through a C-to-C formal 1,3-acyl migration via a solvent cage-nested acylium cation.

Improved cycle stability and high-rate capability of LiNbO3-coated Li3VO4 as anode material for lithium-ion battery

Lithium vanadate (Li3VO4) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li3VO4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, we report the synthesis of lithium niobate LiNbO3-coated Li3VO4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li3VO4. To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.

Investigations of swift heavy ion induced thermoluminescence effect, trapping parameter analysis, and density functional theory of MgB4O7: Eu phosphor

The present work reports swift heavy ion (SHI) induced thermoluminescence (TL) dosimetric properties and density functional theory (DFT) studies of Eu doped MgB4O7 phosphor. Comparative investigations of structural, and luminescent properties of MgB4O7:Eu phosphor upon irradiation by 100 MeV Ag7+ and Ni7+ ion beams at the varied fluence range from 1 × 1010 ion/cm2 to 5 × 1012 ion/cm2 are presented systematically. Eu doped MgB4O7 phosphor is prepared by facile hydrothermal method. X-ray diffraction pattern of the material reveals its orthorhombic structure with crystallite size of ∼30 nm. Fourier transform infrared spectroscopy (FTIR) studies demonstrate loss of crystallinity of material after the SHI irradiations. Correlation of stopping powers and projectile range calculations is performed using SRIM software. The investigated photoluminescence properties show emission bands located in the orange-red region with prominent peaks centered at ∼593 nm and ∼625 nm corresponding to 5D0→7F1 and 5D0→7F2 transitions of Eu3+ion. The influence of ion beam fluence on the photoluminescence properties has been explored. Variation in the intensity of the PL peaks without any shift in the peak positions is observed at different ion fluence. The TL glow curve of phosphor exhibits two major dosimetric peaks (a) at 185 °C and 275 °C and (b) at 172 °C and 273 °C upon Ag7+ and Ni7+ ion beam irradiation respectively. The phosphor shows fairly good linear dose response in the range of 1 × 1010 ion/cm2 to 5 × 1012 ion/cm2. Fading measurements reveal 10% and 12% fading for the irradiation of Ag7+ and Ni7+ ions respectively in two months. Trapping parameter calculations of SHI irradiated phosphors are carried out via various TL glow curve analysis methods such as, peak shape method, whole glow peak method, and glow curve deconvolution method. Efficient thermoluminescence properties of MgB4O7:Eu make it a potential phosphor material and promise to provide avenue into swift heavy ion dosimetry applications. DFT computational studies performed to obtain the electronic structure of Eu doped MgB4O7 phosphor support the experimental results of crystal structure, symmetry and electronic structure studies.

Reusable HNO Sensors Derived from Cu Cyclam: A DFT Study on the Mechanistic Origin of High Reactivity and Favorable Conformation Changes and Potential Improvements.

Nitroxyl (HNO) exhibits unique favorable properties in regulating biological and pharmacological activities. However, currently, there is only one Cu-based HNO sensor that can be recycled for reusable detection, which is a Cu cyclam derivative with a mixed thia/aza ligand. To elucidate the missing mechanistic origin of its high HNO reactivity and subsequent favorable conformation change toward a stable CuI product that is critical to be oxidized back by the physiological O2 level for HNO detection again, a density functional theory (DFT) computational study was performed. It not only reproduced experimental structural and reaction properties but also, more importantly, revealed an unknown role of the coordination atom in high reactivity. Its conformation change mechanism was found to not follow the previously proposed one but involve a novel favorable rotation pathway. Several newly designed complexes incorporating beneficial effects of coordination atoms and substituents to further enhance HNO reactivity while maintaining or even improving favorable conformation changes for reusable HNO detection were computationally validated. These novel results will facilitate the future development of reusable HNO sensors for true spatiotemporal resolution and repeated detection.

Support Effect of Boron Nitride on the First N-H Bond Activation of NH3 on Ru Clusters.

Support effect is an important issue in heterogeneous catalysis, while the explicit role of a catalytic support is often unclear for catalytic reactions. A systematic density functional theory computational study is reported in this paper to elucidate the effect of a model boron nitride (BN) support on the first N-H bond activation step of NH3 on Run (n = 1, 2, 3) metal clusters. Geometry optimizations and energy calculations were carried out using density functional theory (DFT) calculation for intermediates and transition states from the starting materials undergoing the N-H activation process. The primary findings are summarized as follows. The involvement of the model BN support does not significantly alter the equilibrium structure of intermediates and transition states in the most favorable pathway (MFP). Moreover, the involvement of BN support decreases the free energy of activation, ΔG≠, thus improving the reaction rate constant. This improvement is more obvious at high temperatures like 673 K than low temperatures like 298 K. The BN support effect leading to the ΔG≠ decrease is most significant for the single Ru atom case among all three cases studied. Finally, the involvement of the model BN may change the spin transition behavior of the reaction system during the N-H bond activation process. All these findings provide a deeper insight into the support effect on the N-H bond activation of NH3 for the supported Ru catalyst in particular and for supported transition metal catalysts in general.

A photoelectrocatalytic system as a reaction platform for selective radical-radical coupling.

The selection of electrode material is a critical factor that determines the selectivity of electrochemical organic reactions. However, the fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate a photoelectrocatalytic (PEC) system as a promising reaction platform for the selective radical-radical coupling reaction owing to the inherent charge-transfer properties of photoelectrocatalysis. As a model reaction, the radical trifluoromethylation of arenes is shown on hematite photoanodes without employing molecular catalysts. The PEC platform exhibited superior mono- to bis-trifluoromethylated product selectivity compared to conventional electrochemical methods utilizing conducting anodes. Electrochemical and density functional theory (DFT) computational studies revealed that controlling the kinetics of anodic oxidation of aromatic substrates is essential for increasing reaction selectivity. Only the PEC configuration could generate sufficiently high-energy charge carriers with controlled kinetics due to the generation of photovoltage and charge-carrier recombination, which are characteristic features of semiconductor photoelectrodes. This study opens a novel approach towards selective electrochemical organic reactions through understanding the intrinsic physicochemical properties of semiconducting materials.

Acetoxy Group-Directed Regioselective C2 Alkenylation of Indoles via Pd-Ag Bimetallic Catalysis.

Regioselective C-H functionalizations of indoles reported to date with directing groups at C3 mainly rely on functional groups that are linked to the indole via C-C bonds. However, groups that are linked to the indole core by C-X linkages are also attractive due to the possibility of further modifications of the C-X bond. Herein, we report a 3-acetoxy directing group for the regioselective C2 alkenylation of indoles via a C-H activation-based, cross-dehydrogenative, oxidative Heck-type reaction. The reaction is catalyzed by Pd(II) and Ag(I) with stoichiometric Cu(II) as the oxidant and provides the 2-alkenylated indoles in yields of 52-84%. The reaction conditions are compatible with several functional groups at different positions as well as different N-protecting groups or free NH groups on the indole core. With respect to the alkene coupling partners, the reactions are successful with acrylates, vinyl sulfates, and phosphates. Specifically designed experiments, as well as density functional theory (DFT) computational studies, reveal that a heterodinuclear [Pd(μ-OAc)3Ag] bimetallic species is the actual catalyst responsible for the C-H alkenylation. A mechanistic path involving this catalytic species was also found to be favorable over other possible pathways for explaining the observed regioselectivity through DFT studies.

Enhanced production and control of liquid alkanes in the hydrogenolysis of polypropylene over shaped Ru/CeO2 catalysts

The hydrogenolysis of polypropylene waste to liquid hydrocarbons offers a promising pathway for the chemical recycling of waste polymers. This work describes the importance of reaction conditions and support morphology to produce high liquid yields with enhanced control of chain length over highly active shaped and non-shaped Ru/CeO2 catalysts. The shaped 2 wt% Ru/CeO2 exhibit high liquid alkane yields (58–81%) when compared to the non-shaped 2 wt% Ru/CeO2 (liquid yield: 34–58%) under optimized reaction conditions (220 °C, 16 h, 30 bar H2). In particular, the 2 wt% Ru/CeO2 nanocube catalyst exhibits the highest activity yielding lighter hydrocarbons. This was rationalized to be a combination of small Ru cluster formation and enhanced metal-support interactions. The influence of larger Ru particles (≥1.5 nm) was confirmed mechanistically using a computational density functional theory study on the hydrogenolysis of pentane (C5) to determine the favorable formation of methane in the non-shaped Ru/CeO2 catalyst.

Ab-initio and density functional theory (DFT) computational study of the effect of fluorine on the electronic, optical, thermodynamic, hole and electron transport properties of the circumanthracene molecule

In this paper, a systematic study of the electronic, optical, thermodynamic, optoelectronic, and nonlinear optical properties with RHF, B3LYP, wB97XD and BPBE methods using the cc-pVDZ basis set have been described to investigate the influence of fluorine (F) atom, which is an electron donor, on the circumanthracene (C40H16). Global reactivity descriptors, hole and electron transport properties were also calculated and compared with other studies on the same molecule. DFT/B3LYP results show that the undoped C40H16 molecule (Egap = 2.135 eV) and its fluorine-doped derivatives (C40F16 and C40H10F6) are semiconducting materials. However, doping the C40H16 molecule with the fluorine atom, partially or totally, favors the creation of a strong donor-acceptor system by considerably reducing its energy gap (Egap). The energy gap values of molecules doped using DFT/B3LYP method are 2.020 eV and 2.081 eV for the C40F16 and C40H10F6 molecules, respectively. These gap energies are below 3 eV, which favours the electronic properties of these molecules. They can be used to design organic solar cells. The nonlinear optical parameters were calculated and compared with those of urea. The values of βmol and μ calculated for C40F16 and C40H10F6 are higher than those of urea; this shows that these two materials have good nonlinear optical properties and therefore, are very good candidates for the design of optoelectronics and photonics devices. Futhermore, our results show that the perfluorination effect on the circumanthracene molecule increases the hole and electron reorganization energies, the vertical and adiabatic electron affinities and ionization energies, the optoelectronic and nonlinear optical properties, the transition excitation energy and the reactivity indices. The reorganization energies values suggest that these materials have promising transport properties. The natural bond orbital (NBO) analysis was also performed to determine the stability energy and charge delocalization in molecules. The theoretical results of the compounds studied in our work are in agreement with the experimental results. This confirms their molecular structures.