Ultrasonic, spectrophotometric and theoretical studies of sigma and PI interactions of iodine with substituted benzene

Baskar, A. Justin Adaikala; Kumar, Ravinder; Solomon, Rajadurai Vijay; Sundararajan, Mahesh; Kannappan, V.; Singh, D. Roop; Jaccob, Madhavan

doi:10.1039/c5ra03297k

Cited by 17 publications

(3 citation statements)

References 71 publications

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“…To calculate the vertical electronic excitation energies and other absorption properties from the ground-state optimized structure, the time dependent-density functional theory (TDDFT) method was employed. Furthermore, Bader’s quantum theory of atoms in molecules (QTAIM) analysis was performed to quantify the nature of noncovalent interactions at a molecular level. − The self-consistent reaction field-polarizable continuum model (SCRF-PCM) was exploited to assess the THF solvent effect in the simulated absorption spectrum.…”

Section: Methodsmentioning

confidence: 99%

Pyrene-Based Chemosensor for Picric Acid—Fundamentals to Smartphone Device Design

et al. 2019

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Developing a fluorescent probe for the selective and sensitive detection of explosives is a topic of continuous research interest. Additionally, underlying the principles behind the detection mechanism is indeed providing substantial information about the design of an efficient fluorescence probe. In this context, a pyrene-tethered 1-(pyridin-2-yl)imidazo[1,5-a]pyridine-based fluorescent probe (TL18) was developed and employed as a fluorescent chemosensor for nitro explosives. The molecular structure of TL18 was well-characterized by NMR and EI-MS spectrometric techniques. UV–visible absorption, steady-state, and time-resolved fluorescence spectroscopic techniques have been employed to explicate the photophysical properties of TL18. The fluorescent nature of the TL18 probe was explored for detection of nitro explosives. Intriguingly, the TL18 probe was selectively responsive to picric acid over other explosives. The quantitative analysis of the fluorescence titration studies of TL18 with picric acid proved that the probe achieved a detection limit of 63 nM. Further, DFT and QTAIM studies were used to establish the nature of the sensing mechanism of TL18. The hydrogen-bonding interactions are the reason for the imperative sensing property of TL18 for picric acid. Thus, our experimental and theoretical studies provide an adequate and appropriate prerequisite for an efficient fluorescent probe. Furthermore, a smartphone-interfaced portable fluorimeter module is developed to facilitate sensitive and real-time sensing of picric acid. This portable module was capable of detecting picric acid down to 99 nM. Eventually, these studies will have a significant impact on development and application of a new class of chemosensors for detection of explosives.

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Section: Methodsmentioning

confidence: 99%

Pyrene-Based Chemosensor for Picric Acid—Fundamentals to Smartphone Device Design

et al. 2019

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“…46 A large number of liquid mixtures with charge-transfer and hydrogen-bonded complexes were studied through ultrasonic methods, and their stability were analyzed by the formation constants determined accurately using this equation in recent years. 13,[16][17][18][19][20][21][22][23][24][25]30 2.2. Quantum Computational Method.…”

Section: Ultrasonic Studymentioning

confidence: 99%

“…The requirements of solvents depend on (i) the cosolvent effect, (ii) ability of a solvent mixture to dissolve reactants easily, (iii) varied evaporative nature, and (iv) multifunctional properties. There are reports that the weak interactions, such as π–π, CH−π, NH−π, and OH−π, are favored, and steric effects, such as Pauli repulsion and the mesomeric effect, hinder the conventional intermolecular hydrogen bonding. − We have successfully correlated the interaction energies of the dimer and molecular complexes computed by DFT studies with stability constants calculated by the Kannappan equation using the measured values of ultrasonic velocities for halogen-bonded systems, hydrogen-bonded mixtures, and charge-transfer complexes to quantify the intermolecular interactions among various liquid mixtures. − …”

Section: Introductionmentioning

confidence: 99%

Exploring the Steric Effect in the Formation of Hydrogen Bonded Complexes of Isopropyl Amine with Aryl Ethers in n-Hexane

Hussain,

Kumar,

Mohamed

et al. 2023

J. Chem. Eng. Data

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Hydrogen bonded complexes of isopropylamine (IPA) with two aromatic ethers, namely, anisole (ANI) and diphenyl ether (DPE), are analyzed from the results obtained from acoustical parameters and density functional theory (DFT) computations. This type of investigation envisages the presence of various interactions existing in these complexes. The measurements of speed of sound (u), density (ρ), and dynamic viscosity (η) were made accurately for two ternary liquid systems containing equal molality of isopropylamine (IPA) and two structurally different ethers in n-hexane solvent at 303.15 K and 101 kPa pressure. Acoustical and excess parameters were calculated from the measured data. The extent of complex formation increases with concentration and is found to be more in the IPA−ANI system than in the IPA−DPE system. The two aromatic ethers favor the complex formation, though they are found to be relatively less stable than the complexes of these ethers with n-propylamine, which may be due to steric hindrance in IPA and weakening of the complex formation. The association of solute components in the two systems through noncovalent interactions is analyzed comprehensively in this paper at molecular-level insights through DFT parameters. The stable and lowest-energy structures of complexes in n-hexane medium were obtained through DFT. Bond parameters and the energy of complexation were analyzed. The data obtained from both the ultrasonic study and DFT method are comparable and showed structural dependence on molecular association in the two systems. This study also confirms the dominance of the steric effect over the inductive effect in the IPA−DPE system compared to that in the IPA−ANI system.

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Computational Unravelling of the Role of Alkyl Groups on the Host‐Guest Complexation of Pillar[5]arenes with Neutral Dihalobutanes

et al. 2018

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Density Functional Theory (DFT) calculations have been carried out to understand the electronic structure and non-covalent interactions within host-guest complexes between 1,4-dihalobutanes (DHBs) and alkylated pillar[5]arenes (P5 A). Binding energies show that the propyl substituted P5 A are found to have greater binding abilities than that of P5 A with smaller alkyl chains. Among the halogens, dibromobutane is found to have higher binding energy compared to difluoro and dichloro butanes respectively. Contribution of different molecular units towards the frontier molecular orbitals has been studied to gain insights into the role of each segment at the molecular level. Electrostatic potential maps are examined to draw clues on the nature of active sites for the inclusion phenomena. Non-covalent interactions (NCI) present in these host-guest complexes are addressed from NCI analysis based reduced density gradient method. In order to characterize these weak interactions, Bader's Quantum Theory of Atoms In Molecules (QTAIM) analysis is utilized. Our results reveal that though the hydrogen bonding patterns in P5 A inclusion complexes are collapsed upon alkylation, a new set of X-HÀC interactions stabilize these DHBs along with other CÀH-p interactions in the alkylated P5 A inclusion complexes. Overall, the present study sheds light on the importance of the alkyl chain and handling non-covalent interactions carefully to tune the binding ability of P5 A.

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Ultrasonic, spectrophotometric and theoretical studies of sigma and PI interactions of iodine with substituted benzene

Abstract: The acoustical method shows the ability to study the structure, energetics and spectroscopic aspects of charge transfer complexes of three different benzenoid compounds with iodine and is supported by the UV-Visible and DFT methods.

Cited by 17 publications

References 71 publications

Pyrene-Based Chemosensor for Picric Acid—Fundamentals to Smartphone Device Design

Pyrene-Based Chemosensor for Picric Acid—Fundamentals to Smartphone Device Design

Exploring the Steric Effect in the Formation of Hydrogen Bonded Complexes of Isopropyl Amine with Aryl Ethers in n-Hexane

Computational Unravelling of the Role of Alkyl Groups on the Host‐Guest Complexation of Pillar[5]arenes with Neutral Dihalobutanes

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