Theoretical investigation of the static (hyper)polarizabilities and reorganization energy of 4,5-dicyanoimidazole chromophore and derivatives containing benzene rings and a saturated bridge

Marcano, Emildo; Squitieri, Emilio; Murgich, Juan; Soscún, Humberto

doi:10.1016/j.comptc.2015.01.013

Cited by 8 publications

(4 citation statements)

References 36 publications

(57 reference statements)

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“…In fact, the dipole moment follows the same sequence at a given family of isomers and therefore the CHELPG charge results endorse the trends observed for dipole moments; that is, the ICT trend is enhanced for augmented donating groups. Similar observations were discussed by Marcano and coworkers for 4,5-dicyanoimidazole chromophore when they modified the donor group appended to this unsaturated molecular system associating NBO charges with ICT process.…”

Section: Resultssupporting

confidence: 83%

Strong Solvent Effects on the Nonlinear Optical Properties of Z and E Isomers from Azo-Enaminone Derivatives

et al. 2016

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We calculated the nonlinear optical properties of 24 azo-enaminone derivatives, incorporating solvent effects on their geometric and electronic structure, to assess the impact of the environment on these properties. Namely, we incorporated chloroform, tetrahydrofuran, acetone, ethanol, methanol, and dimethyl sulfoxide in our calculations and compared our results incorporating solvent effects with our gas-phase calculations. To account for the electron correlation effects on NLO properties, we performed the calculations at MP2/6-31G(p)//MP2/6-31G(d) level set. The polarizable continuum model was used to simulate the presence of the solvent. The exponents of p extra functions added to heavy atoms were obtained, imposing the maximization of the first hyperpolarizability. Two structural configurations (Z and E) of azo-enaminones were investigated to assess the isomeric effects of the electric properties. Our results show that both solvent polarity and relative strength of the donor groups have a significant impact on the electric properties but more strikingly on the first hyperpolarizability β.

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Section: Resultssupporting

confidence: 83%

Strong Solvent Effects on the Nonlinear Optical Properties of Z and E Isomers from Azo-Enaminone Derivatives

et al. 2016

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“…Furthermore, it provides details of charge transfer in a conjugative molecular architechtonics . Specifically, in this case, it has been performed using methanol solvent to validate intramolecular charge transfer interactions.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, it provides details of charge transfer in a conjugative molecular architechtonics. 50 Specifically, in this case, it has been performed using methanol solvent to validate intramolecular charge transfer interactions. A number of interactions with large E (2) value have been reported which illustrate the intensive interaction between electron donors and electron acceptors.…”

Section: Reorganization Energies Reorganization Energy (λ)mentioning

confidence: 99%

From Molecules to Devices: A DFT/TD-DFT Study of Dipole Moment and Internal Reorganization Energies in Optoelectronically Active Aryl Azo Chromophores

et al. 2018

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The present paper elicits a very useful, computational exploration of molecular architectonics of benzothiazole scaffold. The investigation elucidates hopping transport phenomenon in donor–acceptor ensembles lying within a same molecule, comprising an azo group as the core entity. In depth electronic and charge transfer behavior of certain substituted aryl azo benzothiazoles (organic π conjugated) considering notions of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) has been investigated. Moreover, the effect of structural variation in aryl azo moiety (−CF3, −SCH3) in presence/absence of solvent has been examined. Also, the impact of disparate solvents namely, polar protic, polar aprotic, and nonpolar solvents has been deduced. Interestingly, results indicate that (E)-2-((4-(trifluoromethyl)phenyl)diazenyl)benzo[d]thiazole (BAF) and (E)-2-(phenyldiazenyl)benzo[d]thiazole (BAB) have affirmed to be the promising candidates for the organic charge transfer material in organic light emitting diodes (OLEDs). It was observed that the substituent (−SCH3) deeply perk up the properties of resulting compound, i.e., (E)-2-((4-(methylthio)phenyl)diazenyl)benzo[d]thiazole (BAS) which demonstrated to be an efficient entrant for photovoltaic devices (dye sensitized solar cells (DSSCs)) as dictated by the internal reorganization energies. Furthermore, in order to substantiate these results vis-à-vis to gain a deep insight to consider these molecules as powerful hole/electron carrier mobilizer, their electron density has also been computed. Results obtained by natural bond orbital (NBO) analysis, provide a strong support to the intramolecular charge transfer properties (ICT). An unprecedented explanation of change in the dipole moment substantiates the ICT properties. Besides, HOMO–LUMO gaps, ionization potentials (IPs), electron affinities (EAs), chemical hardness, and light harvesting efficiency (LHE) have been computed to comprehend the nature of the moiety in a more ameliorate way. Also, vibrational findings of BAS placed it as a propitious candidate for in vivo biosensing applications.

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“…Solvent dielectric effects were considered using the popular implicit conductor-like polarizable continuum model (C-PCM) [43] which has become an increasingly useful tool for predicting the electronic structures of ground and excited states of molecules in solution [44]. The internal reorganization energies, which is one of the important parameters for determining the charge transporting properties, have been calculated in the gas phase at the CAM-B3LYP/6-31G(d,p) [45] level for the studied YCTCs D1-D8.…”

Section: Computational Detailsmentioning

confidence: 99%

DFT and TD-DFT study on quadratic NLO response and optoelectronic activity in novel Y-shaped imidazole-based push-pull chromophores

Zaitri

Mekelleche

2021

J Mol Model

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A theoretical analysis of a series of imidazole-based Y-shaped chromophores, D1-D8, is performed in order to investigate their non(linear) optical, fluorescence, and charge-transport properties. The calculations have been carried out employing DFT and TD-DFT methods at CAM-B3LYP and M06-2X levels of theory. FMO analysis reveals that in ground state, highest occupied molecular orbital is localized on the 4,5-dimethylanilino donor moiety and imidazole core while lowest unoccupied molecular orbital spreads on p-linker and nitro acceptor moieties. Vertical absorption and fluorescence transitions are characterized as intramolecular charge transfer and maximum absorption and fluorescence wavelengths show that by changing the p-bridge to the imidazole C2, we can tune fluorescence color from cyan to orange. Calculated (hyper)polarizabilities show that elongation of πlinker by polarizable subunits, such as double bonds or heteroaromatic rings, increases significantly the nonlinear response and shifts the charge-transfer band bathochromically. Calculated reorganization energies indicate that the studied compounds are hole-transporting materials rather than electron-transporters. Interestingly, D7 and D8, with higher hyperpolarizabilities, are predicted to be potent candidates for NLOdevices while D5 and D8 molecules are expected to be promising candidates for luminescent materials and good hole-transport materials for organic light emitting diodes.

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Theoretical investigation of the static (hyper)polarizabilities and reorganization energy of 4,5-dicyanoimidazole chromophore and derivatives containing benzene rings and a saturated bridge

Cited by 8 publications

References 36 publications

Strong Solvent Effects on the Nonlinear Optical Properties of Z and E Isomers from Azo-Enaminone Derivatives

Strong Solvent Effects on the Nonlinear Optical Properties of Z and E Isomers from Azo-Enaminone Derivatives

From Molecules to Devices: A DFT/TD-DFT Study of Dipole Moment and Internal Reorganization Energies in Optoelectronically Active Aryl Azo Chromophores

DFT and TD-DFT study on quadratic NLO response and optoelectronic activity in novel Y-shaped imidazole-based push-pull chromophores

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