Charge-transfer complexes of hypoglycemic sulfonamide with π-acceptors: Experimental and DFT-TDDFT studies

An exceptionally unique, easy-to-prepare, and economic charge transfer complex (CTC), [(IMH) + (PA) − ], was synthesized as a highly selective real-time colorimetric chemosensor material for nitro explosive nitrobenzene (NB) and Co 2+ ion. Co 2+ and NB are highly potential toxic and hazardous beyond the exposure limits and also classified as carcinogens (group 2B) by IARS and United States Environmental Protection Agency. Unusual sensing ability with appreciatively low detection limits of 0.114 and 0.589 ppb for NB and Co 2+ ion, respectively, in the aqueous medium of dimethyl sulfoxide has been reported for the first time among this class of complexes reported so far. The mechanism of the tremendous sensing behavior of this material as chemosensor was ascertained by static quenching mechanism, Dexter electron transfer, and Forster resonance energy transfer dynamic quenching mechanism, which was supported by spectral overlapping and density functional theory (DFT) (B-3LYP/def2-SVP) calculations. Real-time colorimetric sensing behavior of chemosensor was demonstrated by the naked eye test and prestained paper Co 2+ strip test. Job’s plot and comparative Fourier transform infrared (FTIR) study between CTC and CTC–Co 2+ complex revealed the coordination mode between CTC and Co 2+ ion and 2:1 stoichiometry. This sensing material [(IMH) + (PA) − ] was synthesized with donor imidazole (IM) and acceptor picric acid (PA), and its characterization was achieved by experimental (single-crystal X-ray diffraction, thermal gravimetric analysis–differential thermal analysis, FTIR, and UV–vis studies) and theoretical methods [DFT/TD-DFT calculations, comparing experimental–theoretical data and obtaining MEP map along with electronic energy gap of HOMO → LUMO (Δ E = 3.545 eV) and Hirshfeld surfaces analysis]. The SC-XRD confirms the composition and bonding features, which show hydrogen bond via N + –H···O – between IM and PA. This N + –H···O – interaction plays a significant role in Co 2+ binding, proving this method of synthesizing CTC as a chemosensor to be a novel approach.

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“…Also, divergences in thermogram of [(IMH) + (PA) − ] was noted from IM and PA, which assures the formation of [(IMH) + (PA) − ]. 46…”

Section: Results and Discussionmentioning

confidence: 99%

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co²⁺: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Khan

Shakya

2019

ACS Omega

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“…The oscillator strength (f) (Soltani et al, 2019), transition dipole moment (μ) (Voigt and Reid, 1964), resonance energy (RN) (Briegleb, 1961), ionization potential (Aloisi and Pignataro, 1973) and transition energy (ECT) (Briegleb and Czekalla, 1960) values of the complex were determined from these equations:…”

Section: Physicochemical Parametersmentioning

confidence: 99%

Study of Charge transfer complexes of chlorothiazide

Ibrahim

Adam

Allam

2021

Aswan University Journal of Environmental Studies

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The CT-complexes of chlorothiazide (n-donor) with picric acid, 3, 5-dinitrobenzoic acid (piacceptor) and iodine (sigma-acceptor) were investigated at different temperatures and solvents. These complexes were investigated in polar solvents (methanol, acetonitrile) and nonpolar solvents (dichloromethane and chloroform). The structures of the CT-complexes were studied by 1HNMR, infrared spectra and elemental analyses. The donation method was occurred from the lone pair of electron of nitrogen atom in chlorothiazide to pi-acceptors (n→ π*) and to sigmaacceptor (n-σ). Scanning electronic microscopy (SEM) shows images of chlorothiazide with 3,5dinitrobenzoic acid, indicates that the produced complex is crystalline with a rod-like shape as the major crystals shapes. The molecular composition of the charge transfers complexes was 1:1 ratio (donor: acceptor) which determined by spectrophotometric titration. The extinction coefficient, εCT, the formation constant, KCT, transition dipole moment (μ), the oscillator strength (f), resonance energy (RN), ionization potential IP and transition energy (ECT) values of the complex were calculated.

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“…Complexation through the CT mechanism enables a long list of applications including studying binding mechanisms of pharmaceutical receptors, studying the pharmacodynamics and thermodynamics of molecules, and anti-inflammatory, antitumor, and antimicrobial studies [ [48] , [49] , [50] , [51] , [52] , [53] , [54] , [55] , [56] , [57] , [58] , [59] , [60] , [61] , [62] , [63] , [64] , [65] , [66] ]. Given the constant increase in the number and types of applications involving CT complexation and the concomitant increase in relevance and attention, extensive research efforts have been dedicated to characterizing the crystallographic, thermodynamic, kinetic, photophysical, and spectral characteristics of CT complexation [ [67] , [68] , [69] , [70] , [71] , [72] , [73] , [74] , [75] , [76] , [77] , [78] , [79] , [80] , [81] , [82] , [83] , [84] , [85] , [86] , [87] , [88] , [89] , [90] , [91] , [92] , [93] , [94] , [95] , [96] , [97] , [98] , [99] , [100] , [101] , [102] , [103] , [104] , [105] , [106] , [107] ,…”

Section: Introductionmentioning

confidence: 99%

Charge-transfer chemistry of azithromycin, the antibiotic used worldwide to treat the coronavirus disease (COVID-19). Part I: Complexation with iodine in different solvents

Adam

Saad

Alsuhaibani

et al. 2021

Journal of Molecular Liquids

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Around the world, the antibiotic azithromycin (AZM) is currently being used to treat the coronavirus disease (COVID-19) in conjunction with hydroxychloroquine or chloroquine. Investigating the chemical and physical properties of compounds used alone or in combination to combat the COVID-19 pandemic is of vital and pressing importance. The purpose of this study was to characterize the charge transfer (CT) complexation of AZM with iodine in four different solvents: CH 2 Cl 2 , CHCl 3 , CCl 4 , and C 6 H 5 Cl. AZM reacted with iodine at a 1:1 M ratio (AZM to I 2 ) in the CHCl 3 solvent and a 1:2 M ratio in the other three solvents, as evidenced by data obtained from an elemental analysis of the solid CT products and spectrophotometric titration and Job's continuous variation method for the soluble CT products. Data obtained from UV–visible and Raman spectroscopies indicated that AZM strongly interacted with iodine in the CH 2 Cl 2 , CCl 4 , and C 6 H 5 Cl solvents by a physically potent n→σ* interaction to produce a tri-iodide complex formulated as [AZM·I + ]I 3 − . XRD and TEM analyses revealed that, in all solvents, the AZM-I 2 complex possessed an amorphous structure composed of spherical particles ranging from 80 to 110 nm that tended to aggregate into clusters. The findings described in the present study will hopefully contribute to optimizing the treatment protocols for COVID-19.

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Charge-transfer complexes of hypoglycemic sulfonamide with π-acceptors: Experimental and DFT-TDDFT studies

Cited by 45 publications

References 63 publications

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co²⁺: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co²⁺: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Study of Charge transfer complexes of chlorothiazide

Charge-transfer chemistry of azithromycin, the antibiotic used worldwide to treat the coronavirus disease (COVID-19). Part I: Complexation with iodine in different solvents

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Charge-transfer complexes of hypoglycemic sulfonamide with π-acceptors: Experimental and DFT-TDDFT studies

Cited by 45 publications

References 63 publications

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co2+: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co2+: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Study of Charge transfer complexes of chlorothiazide

Charge-transfer chemistry of azithromycin, the antibiotic used worldwide to treat the coronavirus disease (COVID-19). Part I: Complexation with iodine in different solvents

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Product

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Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co²⁺: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights

Exploring Colorimetric Real-Time Sensing Behavior of a Newly Designed CT Complex toward Nitrobenzene and Co²⁺: Spectrophotometric, DFT/TD-DFT, and Mechanistic Insights