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In this study, a series of non-fused thiophene ring-based small molecular acceptors (4T1-4T7) of A-D-A type are developed by the replacement of the end-groups of the 4TR molecule. The optoelectronic characteristics of the 4TR and 4T1-4T7 molecules are investigated employing the MPW1PW91 functional with the 6-31G (d,p) basis set, and solvent-state computations are studied using the TD-SCF. All the parameters estimated in this research are improved to a substantial level for the developed molecules as compared to the 4TR molecule

Coordination complexes are interesting materials for nonlinear optical (NLO) applications due to their large hyperpolarizability values. Moreover, switchable NLO response is also important in coordination complexes. Herein, we report two state ON-OFF switchable NLO contrast of coordination complexes of Fe and Co containing isomeric ligands. The optical, UV-visible, and electronic properties besides the "ON-OFF" switching effect are calculated using the CAM-B3LYP/6-31+G (d) method. The NLO responses of ligand-metal isomers are qualitatively evaluated through variation in charge transference (CT) style through TD-DFT. The higher

A series of small pure Au

Porous organic cages have shape persistent cavities which provide a suitable platform for encapsulation of guest molecules with size suitably fitting to the cavity. The interactions of the guest molecule with the porous organic cage significantly alter the properties of the guest molecule. Herein, we report the effect of encapsulation on the kinetics of various organic transformations including 2 + 4 cycloaddition, 1,5-sigmatropic, 6π-electrocyclization, ring expansion, cheletropic, dyotropic, trimerization and tautomerization reactions. Non-bonding interactions are generated between the CC2 cage and encapsulated species. However, the number and nature/strength of interactions are different for reactant and TS with the CC2 cage and this difference detects the reaction to be accelerated or slowed down. A significant drop in the barrier of reactions is observed for reactions involving strong interactions of the transition state within the cage. However, for some reactions such as the Claisen rearrangement, reactants are stabilized more than the transition state and therefore an increase in activation barrier is observed. Furthermore, non-covalent analyses of all transition states (inside the cage) confirm the interaction between the CC2 cage and substrate. The current study will promote further exploration of the potential of other porous structures for similar applications.

DFT calculations are carried out to investigate nonlinear optical (NLO) properties of superhalogen (BCl4) and superalkali (NLi4) doped graphitic carbon nitride (GCN). It is noted that the geometries of doped GCN are sufficiently stable. The energy gap for GCN is 3.89 and it reduces to 0.53 eV in our designed molecule G4. Change in the dipole and transition dipole moment is observed along with small transition energies which are responsible for higher hyperpolarizabilities. Doped GCN has larger first and second hyperpolarizabilities which are basic requirements for NLO response. The second hyperpolarizability of GCN enhances from 1.59 × 104 to 2.53 × 108 au when doping with BCl4 and NLi4. TD-DFT calculations show the absorption maxima of doped GCN range from 700 nm to 1350 nm. EDDM analysis provides information on electronic distribution from excited to ground state. All these consequences show doped GCN can be a promising NLO material.

Herein, the structural, electronic, thermodynamic, linear and nonlinear optical properties of inorganic electrides, generated by alkali metal doping in group II–VI Ca12O12 fullerene, are studied. Endohedral doping of alkali metal leads to the formation of electrides whereas no such phenomenon is seen for exohedral doping. The electride nature of the endohedral fullerenes is confirmed through the analysis of frontier molecular orbitals. The results show that doping of alkali metal atoms leads to a reduction of the HOMO–LUMO gap and increase of the dipole moment, polarizability and hyperpolarizability of nanocages. Doping causes shifting of electrons from alkali metal atoms towards the Ca12O12 nanocage, which serve as excess electrons. Furthermore, the participation of excess electrons for enhancing the NLO response of these nanocages has been confirmed through the calculation of hyperpolarizability (βo). For exploring the controlling factors of hyperpolarizability, a two level model has been employed and the direct relation of hyperpolarizability with Δμ & fo, while an inverse relation of hyperpolarizability with ΔE has been studied. The electrides possess remarkable nonlinear response where the highest hyperpolarizability can reach up to 1.0 × 106 a.u. for endo-K@Ca12O12. This electride has the lowest ΔE of 0.63 eV among all compounds studied here. These intriguing results will be expedient for promoting the potential applications of the Ca12O12-based nano systems in high-performance nonlinear optical (NLO) materials.

In this study, the nonlinear optical (NLO) response of alkali metal atom (Li, Na and K) and their corresponding superalkali (Li3O, Na3O and K3O) doped six membered cyclic thiophene (6CT) has been explored. The optimized geometries of complexes; Li@6CT, Na@6CT, K@6CT, Li3O@6CT, Na3O@6CT and K3O@6CT depict that the superalkalis and alkali metals interact through the active cavity of 6CT. Interaction energies reveal that superalkalis have higher interaction with 6CT than alkali metals. The nonlinear optical (NLO) response of the reported complexes is estimated via both static and dynamic hyperpolarizabilities which are further rationalized by the HOMO–LUMO gap, natural bond orbital (NBO) charge transfer, dipole moment, polarizabilities and βvec. A remarkably high NLO response is computed for Na3O@6CT among all of the complexes. The static hyperpolarizability of the Na3O@6CT complex is 5 × 104 au along with the highest βvec value (2.5 × 104 au). High charge transfer (1.53e−) and small EH–L gap (2.96 eV) is responsible for such a large NLO response. For dynamic NLO responses, electro-optic Pockel's effect (EOPE) and second-harmonic generation (SHG) are explored. A very large quadratic nonlinear optical response (3.8 × 10−12 au) is observed for the Na3O@6CT complex. Moreover, the absorption spectrum of the Na3O@6CT complex shows ultra-high transparency in the ultraviolet and visible regions unlike any other of its counterparts.

Strategies for designing remarkable nonlinear optical materials using excess electron compounds are well recognized in literature to enhance the applications of these compounds in nonlinear optics. In this study, density functional theory simulations are performed to study alkali and alkaline earth metal-doped benzocryptand using the B3LYP/6-31G+(d, p) level of theory. Vertical ionization energies (VIEs), reactivity parameters, interaction energies, and binding energies exposed the thermodynamic stability of these complexes. FMO analysis revealed that HOMO is located on alkali metals having polarized electrons, which are easy to excite. The doping strategy enhanced the charge transfer with low bandgap energy in the range of 0.68-2.23 eV, which is lower than that of the surface BC (5.50 eV). Also, the lower transition energies and higher oscillator strength indicate that these complexes exhibit excellent electronic and optical properties. Non-covalent interaction analysis suggested the presence of van der Waals interactions between dopants and surface. IR analysis provided information about the frequencies of stretching vibrations present in the complexes due to different bonds. UV-vis analysis revealed that all the newly designed excess electron complexes are transparent in the UV region and possessed maximum absorption in the visible and NIR region, ranging from 753.6 to 2150 nm, which is higher than the surface (244 nm). Thus, these complexes have a potential for high-performance NLO materials in the applications of optics. Natural bond orbital analysis (NBO), transition density matrix (TDM), electron density difference map (EDDM), and density of state (DOS) analyses were also performed to study the charge transfer properties. Moreover, these complexes possessed remarkable optoelectronic properties due to a significant increase in the isotropic linear polarizability (

Two-dimensional (2D) monolayer nanomaterials are the thinnest possible membranes with interesting selective permeation characteristics. Among two-dimensional materials, graphenes and hexagonal boron nitride (h-BN) are the most promising membrane materials, which can even allow the separation of proton isotopes. The current work aims at understanding the higher reported permeability of h-BN by sequential doping of B and N atoms in graphene nanoflakes. The kinetic barriers were calculated with two different models of graphenes; coronene and dodecabenzocoronene

In the current study, a covalent triazine framework (CTF-0) was evaluated as an electrochemical sensor against industrial pollutants i.e., O3, NO, SO2, SO3, and CO2.

Herein, the geometric, electronic, and nonlinear optical properties of excess electron zintl clusters Ge5AM3, Ge9AM5, and Ge10AM3 (AM = Li, Na, and K) are investigated.

This research study addresses the computational simulations of optical and nonlinear optical (NLO) characteristics of silver (Ag) cluster doped graphyne (GY) complexes. By precisely following DFT and TD-DFT hypothetical computations, in-depth characterization of GY@Ag

The geometric, thermodynamic and electronic properties of Pd–graphene nanocomposites are comprehensively studied through quantum mechanical methods. Geometries of these clusters are optimized with the well-calibrated Minnesota functional M06-2X. The adsorption energies calculated at the M06-2X/LANL2DZ level show better agreement with those calculated from MP2/ANO-RCC-VDZP. Two different representative models for graphene, coronene and hexabenzocoronene, are used. The adsorption energies analysis reveals that the interaction energies increase with the size of the adsorbed cluster. However, for Pdn/hexabenzocoronene, the interaction energies show a sudden drop at Pd8/hexabenzocoronene. The difference in behavior between the interaction energies of Pdn/hexabenzocoronene and Pdn/coronene is attributed to the edge effect present in coronene. The electronic properties, including highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), Fermi level, molecular electrostatic potential (MEP), dipole moment, vertical ionization potential (VIP), vertical electron affinity (VEA), chemical hardness (η), softness (S) and chemical potential (μ) are studied. The VIP and VEA reveal that Pdn/coronene clusters are stable in nature with the least reactivity. The HOMO–LUMO energy gaps are reduced with the increase in cluster size. The electronic properties show irregular trends, where the most favorable electronic properties are obtained for Pd7/coronene and Pd10/coronene.

Explosives are quite toxic and destructive; therefore, it is necessary to not only detect them but also remove them. The adsorption behavior of NX3 analytes (NCl3, NBr3 and NI3) over the microporous C2N surface was evaluated by DFT calculations. The nature of interactions between NX3 and C2N was characterized by adsorption energy, NCI, QTAIM, SAPT0, NBO, EDD and FMO analysis. The interaction energies of NX3 with C2N are in the range of −10.85 to −16.31 kcal mol−1 and follow the order of NCl3@C2N > NBr3@C2N > NI3@C2N, respectively. The 3D isosurfaces and 2D-RGD graph of NCI analysis qualitatively confirmed the existence of halogen bonding interactions among the studied systems. Halogen bonding was quantified by SAPT0 component energy analysis. The SAPT0 results revealed that ΔEdisp (56.75%) is the dominant contributor towards interaction energy, whereas contributions from ΔEelst and ΔEind are 29.41% and 14.34%, respectively. The QTAIM analysis also confirmed the presence of halogen bonding between atoms of NX3 and C2N surface. EDD analysis also validated NCI, QTAIM and NBO analysis. FMO analysis revealed that the adsorption of NI3 on the C2N surface caused the highest change in the EHOMO–LUMO gap (from 5.71 to 4.15 eV), and resulted in high sensitivity and selectivity of the C2N surface towards NI3, as compared to other analytes. It is worth mentioning that in all complexes, a significant difference in the EHOMO–LUMO gap was seen when electronic transitions occurred from the analyte to the C2N surface.

Herein, the structural, electronic, thermodynamic, linear and nonlinear optical properties of inorganic electrides, generated by alkali metal doping in group II-VI Ca

In this study, the therapeutic potential of phosphorene as a drug-delivery system for chlorambucil to treat cancer was evaluated. The geometric, electronic and excited state properties of chlorambucil, phosphorene and the phosphorene–chlorambucil complex were evaluated to explore the efficiency of phosphorene as a drug-delivery system. The nature of interaction between phosphorene and chlorambucil is illustrated through a non-covalent interaction (NCI) plot, which illustrated that weak forces of interaction are present between phosphorene and chlorambucil. These weak intermolecular forces are advantageous for an easy offloading of the drug at the target. Frontier molecular orbital analysis revealed that charge was transferred from chlorambucil to phosphorene during excitation from the HOMO to LUMO. The charge transfer was further supplemented by charge-decomposition analysis (CDA). Excited-state calculations showed that the λmax was red-shifted by 79 nm for the phosphorene–chlorambucil complexes. The photo-induced electron-transfer (PET) process was observed for different excited states, which could be well explained visually based on the electron–hole theory. The photo-induced electron transfer suggests that a quenching of fluorescence occurs upon interaction. This study confirmed that phosphorene possesses significant therapeutic potential as a drug-delivery system for chlorambucil to treat cancer. This study will also motivate further exploration of other 2D materials for drug-delivery applications.

Non-fullerene small acceptor molecules have gained significant attention for application in organic solar cells owing to their advantages over fullerene based acceptors. Efforts are continuously being made to design novel acceptors with greater efficiencies. Here, optoelectronic properties of four novel acceptor–donor–acceptor (A–D–A) type small molecules (A1, A2, A3 and A4) were studied for their applications in organic solar cells. These molecules contain an indacenodithiophene central core unit joined to different end capped acceptors through a monofluoro substituted benzothiadiazole (FBT) donor acceptor (DA) bridge. The different end capped acceptor groups are; 2-2(2-ethylidene-5,6-difluoro-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (A1), 2-2(2-ethylidene-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (A2), 2-(5-ethylidene-6-oxo-5,6-dihydrocyclopenta-b-thiophene-4-ylidene)malononitrile (A3), and 2-2(2-ethylidene-5,6-dicyano-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (A4). The calculated optoelectronic properties of the designed molecules were compared with a well-known reference compound R, which was recently synthesized and reported as being an excellent A–D–A type acceptor molecule. All designed molecules showed the appropriate frontier molecular orbital diagram for a charge transfer. A4 shows the highest absorption maximum (λmax) of 858.6 nm (in chloroform solvent), which was attributed to the strong electron withdrawing end-capped acceptor group. Among all of the designed molecules, A3 exhibits the highest open circuit voltages (Voc) which was (1.84 V) with PTB7-Th and (1.76 V) with the P3HT donor polymer. Owing to a lower value of λe with respect to λh, the designed molecules demonstrated superior electron mobilities when compared with reference R. Among all of the molecules, A4 shows the highest electron mobility owing to the lower value of λe compared to R.

Scientists are focusing on non-fullerene based acceptors due to their efficient photovoltaic properties. Here, we have designed four novel dithienonaphthalene based acceptors with better photovoltaic properties through structural modification of a well-known experimentally synthesized reference compound R. The newly designed molecules have a dithienonaphthalene core attached with different acceptors (end-capped). The acceptor moieties are 2-(5,6-difluoro-2-methylene-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (H1), 2-(5,6-dicyano-2-methylene-3-oxo-2,3-dihydroinden-1-ylidene)-malononitrile (H2), 2-(5-methylene-6-oxo-5,6-dihydrocylopenta[c]thiophe-4-ylidene)-malononitrile (H3) and 2-(3-(dicyanomethylene)-2,3-dihydroinden-1-yliden)malononitrile (H4). The photovoltaic parameters of the designed molecules are discussed in comparison with those of the reference R. All newly designed molecules show a reduced HOMO–LUMO energy gap (2.17 eV to 2.28 eV), compared to the reference R (2.31 eV). Charger transfer from donor to acceptor is confirmed by a frontier molecular orbital (FMO) diagram. All studied molecules show extensive absorption in the visible region and absorption maxima are red-shifted compared to R. All investigated molecules have lower excitation energies which reveal high charge transfer rates, as compared to R. To evaluate the open circuit voltage, the designed acceptor molecules are blended with a well-known donor PBDB-T. The molecule H3 has the highest Voc value (1.88 V). TDM has been performed to show the behaviour of electronic excitation processes and electron hole location between the donor and acceptor unit. The binding energies of all molecules are lower than that of R. The lowest is calculated for H3 (0.24 eV) which reflects the highest charge transfer. The reorganization energy value for both the electrons and holes of H2 is lower than R which is indicative of the highest charge transfer rate.

The use of small molecules as chemosensors for ion detection is rapidly gaining popularity by virtue of the advantages it offers over traditional ion sensing methods. Herein we have synthesized a series of acridine(1,8)diones (7a–7l) and explored them for their potential to act as chemosensors for the detection of various anions such as fluoride (F−), acetate (OAc−), bromide (Br−), iodide (I−), bisulfate (HSO4−), chlorate (ClO3−), perchlorate (ClO4−), cyanide (CN−), and thiocyanate (SCN−). Acridinediones were found to be highly selective chemosensors for fluoride ions only. To investigate in detail the mechanism of selective fluoride ion sensing, detailed spectroscopic studies were carried out using UV-visible, fluorescence and 1H NMR spectroscopy. Fluoride mediated (NH) proton abstraction of acridinedione was found to be responsible for the observed selective fluoride ion sensing. Quantum mechanical computational studies, using time dependent density functional theory (TDDFT) were also carried out, whereupon comparison of acridinedione interaction with fluoride and acetate ions explained the acridinedione selectivity for the detection of fluoride anions. Our results provide ample evidence and rationale for further modulation and exploration of acridinediones as non-invasive chemosensors for fluoride ion detection in a variety of sample types.

The effect of alkali metal (Li, Na, and K) doping in aluminum nitride (Al12N12) nanocages is studied through density functional theory (DFT) methods. Six new stable compounds of M@Al12N11 and M@Al11N12 are designed theoretically where alkali metal replaces an atom (Al/N) of a nanocage. The stability of the doped nano-cages is evaluated through binding energy calculations. Doping alkali atom M (M = Li, Na, K) into a nanocage significantly reduces the band gap (HOMO–LUMO gap). Polarizability and first hyperpolarizability are calculated using long range separated methods to evaluate the non-linear optical (NLO) properties of these doped systems. The hyperpolarizability of MAl12N11 nanocages is much higher than that of M@Al11N12 nanocages. The higher hyperpolarizability of M@Al12N11 nanocages is believed to arise from participation of excess diffuse electrons, revealed from PDOS.

New quinoxalinium salts 1–5 have been exploited as chemosensors via naked eye, UV-Vis absorption, fluorescence quenching and 1H NMR experiments. New sensors 1–5 showed a dual mode, nucleophilic addition and a host–guest type complex towards anion (F−, AcO− and ascorbate) detection. Small anions (F−/AcO−) showed nucleophilic addition at the C2 position of the quinoxalinium cation, while larger anions (ascorbate), revealed the formation of a host–guest type complex due to the steric hindrance posed by the C3 of the phenyl ring. Nucleophilic addition of small anions (F−/AcO−) leads to the de-aromatization of the quinoxalinium cation. However in the case of the larger anion, ascorbate, the host–guest type complex formation induces changes in the absorption/fluorescence signals of the quinoxalinium moiety. This selective binding has been confirmed on the basis of the 1H NMR spectroscopic technique, whereupon nucleophilic addition of small anions (F−/AcO−) was confirmed by monitoring the characteristic proton NMR signals of Ha and the methylene protons (CH2), which were clearly shifted in the cases of fluoride and acetate ion addition confirming the de-aromatization and nucleophilic addition. Whereas no such peak shifting was observed in the case of ascorbate ion addition confirming the non-covalent addition of ascorbate. Theoretical insight into the selectivity and complexation behavior of the ascorbate ion with the quinoxaline moiety is gained through density functional theory (DFT) calculations. Moreover, the absorption properties of these complexes are modeled theoretically, and compared with the experimental data. In addition, the thermal decomposition of sensors (1 and 2) has been studied by the means of differential scanning calorimetry (DSC), thermogravimetry (TG), and differential thermogravimetry (DTG) to signify their utility at variable temperatures.

The mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde and ester by H2O2 oxidant was investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Both inner sphere and intermediate sphere mechanisms have been analyzed in the presence and absence of pyridine-2-carboxylic acid (ligand). An intermediate sphere mechanism involving the transfer of hydrogen from alcohol to H2O2 was found to be preferred over the competitive inner sphere mechanism involving β-hydride elimination. Kinetic barriers associated with the intermediate sphere mechanism are consistent with the experimental observations, suggesting that the intermediate sphere mechanism is a plausible mechanism under these reaction conditions. The oxidation of alcohols to aldehydes (first step) is kinetically more demanding than the oxidation of hemiacetals to esters (second step). Changing the oxidant to tert-butyl hydrogen peroxide (TBHP) increases the activation barrier for the oxidation of alcohol to aldehyde by 0.4 kcal mol−1, but decreases the activation barrier by 3.24 kcal mol−1 for oxidation of hemiacetal to ester. Replacement of zinc bromide with zinc iodide causes the second step to be more demanding than the first step. Pyridine-2-carboxylic acid ligand remarkably decreases the activation barriers for the intermediate sphere pathway, whereas a less pronounced inverse effect is estimated for the inner sphere mechanism.

The mechanism of TiCl4 mediated formal [3 + 3] cyclization of 1,3-bis(silyl enol ethers) with 1,3-dielectrophiles is studied at the B3LYP level of density functional theory (DFT) to rationalize the experimental regioselectivity. Methyl and trifluoromethyl substituted 1,3 dielectrophiles are studied theoretically since they show different regioselectivities. Two different mechanisms involving 1,2 and 1,4 addition of 1,3-bis(silyl enol ethers) on 1,3-dielectrophiles are studied for each dienophile. The intramolecular transition metal catalyzed and non-catalyzed dynamic shift of the silyl moiety is also studied. The structure of the 1,3 dienophile and the associated Mulliken charges are the driving forces for different regioselectivities in methyl and trifluoromethyl dienophiles.

Correction for ‘Acridinedione as selective flouride ion chemosensor: a detailed spectroscopic and quantum mechanical investigation’ by Nafees Iqbal et al., RSC Adv., 2018, 8, 1993–2003.