Stoichiometric, Thermodynamic and Computational DFT Analysis of Charge Transfer Complex of 1-Benzoylpiperazine with 2, 3-Dichloro-5, 6-Dicyano-1, 4-benzoquinone

Abbu, Venugopal; Baindla, Naveen; Tigulla, Parthasarathy

doi:10.1007/s10953-019-00847-5

Cited by 33 publications

(9 citation statements)

References 40 publications

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“…33,34 Moreover, it can easily form a charge transfer DDQ-donor complex by reacting with an electron donor. 35,36 Recently, Sun et al demonstrated that DDQ could be a promising p-dopant for triphenylaminebased oligomer HTM named MeO-TPD in solid-state dyesensitized solar cells. 37 Therefore, we employed DDQ as a ptype dopant into spiro-OMeTAD HTL for highly efficient PSCs.…”

Section: Introductionmentioning

confidence: 99%

Strong electron acceptor additive based spiro-OMeTAD for high-performance and hysteresis-less planar perovskite solar cells

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Strong electron acceptor additive based spiro-OMeTAD for high-performance and hysteresis-less planar perovskite solar cells

et al. 2020

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“…Physical Composition of the CT Complex. The molecular composition of the CT complex was determined by applying Job's continuous variations at 617, and 626 nm 23 in both ACN and MeOH medium shown in (Figure 2a). Where maximum absorbance achieved at 0.5 mol fraction indicating 1:1 [(4-DMAP)/(DDQ)] stoichiometry for the complex.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

New Charge Transfer Complex between 4-Dimethylaminopyridine and DDQ: Synthesis, Spectroscopic Characterization, DNA Binding Analysis, and Density Functional Theory (DFT)/Time-Dependent DFT/Natural Transition Orbital Studies

et al. 2021

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A combined experimental and theoretical study of the electron donor 4-dimethylaminopyridine (4-DMAP) with the electron acceptor 2, 3-dichloro-5, 6-dicyano- p -benzoquinone (DDQ) has been made in acetonitrile (ACN) and methanol (MeOH) media at room temperature. The stoichiometry proportion of the charge transfer (CT) complex was determined using Job’s and photometric titration methods and found to be 1:1. The association constant ( K CT ), molar absorptivity (ε), and spectroscopic physical parameters were used to know the stability of the CT complex. The CT complex shows maximum stability in a high-polar solvent (ACN) compared to a less-polar solvent (MeOH). The prepared complex was characterized by Fourier transform infrared, NMR, powder X-ray diffraction, and scanning electron microscopy–energy-dispersive X-ray analysis. The nature of DNA binding ability of the complex was probed using UV–visible spectroscopy, and the binding mode of the CT complex is intercalative. The intrinsic binding constant ( K b ) value is 1.8 × 10 6 M –1 . It reveals a primary indication for developing a pharmaceutical drug in the future due to its high binding affinity with the CT complex. The theoretical study was carried out by density functional theory (DFT), and the basis set is wB97XD/6-31G(d,p), with gas-phase and PCM analysis, which supports experimental results. Natural atomic charges, state dipole moments, electron density difference maps, reactivity parameters, and FMO surfaces were also evaluated. The MEP maps indicate the electrophilic nature of DDQ and the nucleophilic nature of 4-DMAP. The electronic spectrum computed using time-dependent DFT (TD-DFT) via a polarizable continuum salvation approach, PCM/TD-DFT, along with natural transition orbital analysis is fully correlated with the experimental outcomes.

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“…The negative ΔG and ΔH values indicate a spontaneous exothermic CTC complexation reaction. In our case, the calculated ΔG values are two to four times smaller than the changes in the Gibbs free energy for CTC formation in the following cases: [p-nitroaniline:chloranilic acid] CTC ΔG (298 K) = À 23.2 kJ mol À 1 ; [17] [1-benzoylpiperazine:2,3-dichloro-5,6-dicyano-p-benzoquinone] CTC ΔG (293 K) = À 22.48 kJ mol À 1 ; [18] [tioconazole:7,7,8,8-tetracyanoquinodimethane] CTC ΔG (293 K) = À 11.6 kJ mol À 1 . [19] The differences in the compared ΔG°values emphasize that we have dealt with the weak-bonded CTC between the components.…”

Section: ð4þmentioning

confidence: 88%

“…In addition to the fact that we observed no changes in the IR or Raman, or 1 H NMR spectra (see Figure S3-S7), there were no signals in the EPR spectra (which could have taken place during the formation of strong charge transfer complexes and radical ion pair). [17][18][19][20] It indicates once again that a weak CTC was formed.…”

Section: ð4þmentioning

confidence: 99%

The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity

et al. 2020

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A photosensitive charge transfer complex (CTC) is formed between the components of the photopolymer material: the tetra-acrylate monomer synthesized from dihydroxydiphenyl sulfide (TADDS) and a photoinitiator, a cationic sulfonium salt synthesized from diethylthioxanthen-9-one (SSDETX). It allows one to perform laser recording of the microstructures in the hybrid photopolymer material using absorption of CTC at λ = 473 nm. The 1 : 1 molecular composition of CTC was confirmed by applying the Job's method of continuous variation to determine the stoichiometry. The association constant (K AS (278°K) = 17 L mol À 1) was calculated using the modified Benesi-Hildebrand equation. The thermodynamic parameters, such as enthalpy (ΔH = À 15.63 kJ mol), entropy (ΔS°= À 32.6 J mol À 1 K À 1), and the Gibbs free energy (ΔG = À 6.63 kJ mol À 1) were calculated using the Van't Hoff equation. These results indicate that CTC formation is an exothermic reaction. The experimental findings were supplemented by density functional theory (DFT) study of CTCs at the UB3LYP/6-311G level as implemented in the Gaussian 09 software package. Charge transfer excitations were simulated by means of the time-dependent density functional theory (TDDFT) approach. The DFT-calculated spectra agree with the experimental data of spectral and photochemical properties of the [SSDETX-TADDS] CTC.

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Stoichiometric, Thermodynamic and Computational DFT Analysis of Charge Transfer Complex of 1-Benzoylpiperazine with 2, 3-Dichloro-5, 6-Dicyano-1, 4-benzoquinone

Cited by 33 publications

References 40 publications

Strong electron acceptor additive based spiro-OMeTAD for high-performance and hysteresis-less planar perovskite solar cells

Strong electron acceptor additive based spiro-OMeTAD for high-performance and hysteresis-less planar perovskite solar cells

New Charge Transfer Complex between 4-Dimethylaminopyridine and DDQ: Synthesis, Spectroscopic Characterization, DNA Binding Analysis, and Density Functional Theory (DFT)/Time-Dependent DFT/Natural Transition Orbital Studies

The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity

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