Ab initio molecular orbital and density functional study of the C6H6⋅I2 complex in the ground and excited electronic states

Mebel, Alexander M.; Lin, Hsin‐Chieh; Lin, Sheng Hsien

doi:10.1002/(sici)1097-461x(1999)72:4<307::aid-qua13>3.0.co;2-e

Cited by 18 publications

(6 citation statements)

References 48 publications

(34 reference statements)

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“…Indeed, spectroscopic studies of numerous electron donor/acceptor systems showed that the CTband energy correlates with the donor ionization potential. 24 The results observed for the molecules used as precursors in the synthesis of PMOs deserve some comments. When considering TEOS and BTEE, the structures of which are depicted in Scheme 1, the HL-band maxima are at 478 and 472 nm, respectively.…”

Section: Resultsmentioning

confidence: 99%

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

et al. 2009

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Periodic mesoporous organosilicas (PMOs), a relatively new class of mesostructured organic-inorganic hybrid materials already thoroughly characterized as it concerns acidic sites, are studied in the present paper from the viewpoint of electron-rich, potentially basic sites. Iodine was adopted as a probe molecule, as it is known that the spectral shift suffered by the I 2 band in the visible region correlates with the donor strength of solvents and solids. Iodine adsorption on ethyl-and phenylene-containing PMOs was followed by means of UV-visible spectroscopy: the results show that the electron-donor ability of oxygen atoms at the PMO surface is higher than that reported for pure siliceous materials and comparable with that of some basic zeolites, in agreement with the previously reported weaker acidity of hydroxyls. In phenylene-bridged PMOs aromatic rings are the preferential adsorption sites for iodine. Comparison between phenylene-bridged PMOs with different degrees of order in the walls reveals a lower availability of aromatic sites on the ordered surface with respect to the amorphous one.

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Section: Resultsmentioning

confidence: 99%

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

et al. 2009

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“…The nature of the halogen−π interactions of alkyl and aryl halides are important for improving our understanding of their roles in determining molecular orientation in crystals and self-assemblies. A few theoretical studies on the nature of the halogen−π interactions were reported. − The halogen−π interactions of I 2 , ClF, and NCX (X = Cl, Br) were reported. − ,,, Only a few theoretical studies were reported on the nature of the halogen−π interactions of alkyl and aryl halides. The interaction energies of tyrosine with chloro- and bromo-benzene using CCSD(T) calculations were reported .…”

Section: Introductionmentioning

confidence: 99%

Magnitude and Directionality of Halogen Bond of Benzene with C₆F₅X, C₆H₅X, and CF₃X (X = I, Br, Cl, and F)

et al. 2016

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Geometries of benzene complexes with C6F5X, C6H5X, and CF3X (X is I, Br, Cl, and F) were optimized, and their interaction energies were evaluated. The CCSD(T) interaction energies at the basis set limit (Eint) of C6F5X (X is I, Br, Cl, and F) with benzene were -3.24, -2.88, -2.31, and -0.92 kcal mol(-1). Eint of C6H5X (X is I, Br, and Cl) with benzene were -2.31, -1.97, and -1.48 kcal mol(-1). The fluorination of halobenzenes slightly enhances the attraction. Eint of CF3X (X is I, Br, Cl, and F) with benzene (-3.11, -2.74, -2.22, and -0.71 kcal mol(-1)) were very close to Eint of corresponding C6F5X with benzene. In contrast to the halogen bond of iodine and bromine with pyridine (n-type halogen bond acceptor) where the main cause of the attraction is the electrostatic interactions, that of halogen bond with benzene (p-type acceptor) is dispersion interaction. In the halogen bonds with p-type acceptors (halogen-π interactions), the electrostatic interactions and induction interactions are small. The overall orbital-orbital interactions are repulsive. The directionality of halogen bonds with p-type acceptors is very weak, owing to the weak electrostatic interactions, in contrast to the strong directionality of the halogen bonds with n-type acceptors and hydrogen bonds.

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“…Additionally, halogen bonding may be involved in the formation of the benzene−iodine complex. 3,46,48,49 In our previous work, we have used the benzene−iodine system as a real-world example to check whether the DOSD and DAOSD approaches were effective or not in probing an intermolecular interaction. 28,29 Figure S5 presents an FTIR spectrum of a chloroform solution of benzene.…”

Section: Resultsmentioning

confidence: 99%

“…The following possible modes of interaction are considered. Reaction model (1) According to the work by Mebel et al, 48 one benzene molecule and one iodine molecule may form a complex. The equilibrium reaction and the equilibrium constant are listed in eqs S17 and S18 in the Supporting Information, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…As a real-world example, a preliminary analysis using TAGAGS was conducted on FTIR spectra of a benzene/iodine system. The interaction between benzene and iodine has been a chemical and physical curiosity for over 60 years. − Many experimental investigations and theoretical calculations have been devoted to this system. Benesi and Hildebrand observed an absorption band in the UV region that could not be attributed to either benzene monomer or the iodine molecule .…”

Section: Results and Discussionmentioning

confidence: 99%

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Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching

Song

et al. 2022

Anal. Chem.

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A supramolecular complex may be formed by two solutes via a weak intermolecular interaction in a solution. The spectrum of the complex is often inundated by the spectra of the solutes that are not involved in the intermolecular interaction. Herein, a novel spectral analysis approach is proposed to retrieve the spectrum of the supramolecular complex. First, a two-dimensional (2D) asynchronous spectrum is constructed. Then, a genetic algorithm is used to obtain a heuristic spectrum of the supramolecular complex. The heuristic spectrum is a linear combination of the spectrum of the complex and the spectrum of a solute. The coefficients of the linear combination are then obtained, according to which the equilibrium constants are invariant among the sample solutions used to construct the 2D asynchronous spectrum. We have applied the approach to a supramolecular system formed by benzene and I2. In the analysis, several binding models are evaluated, and a benzene molecule interacting with two iodine molecules via halogen bonding turns out to be the only possible model. Hence, the characteristic band of the benzene/I2 supramolecular complex around 1819 cm–1 in the Fourier transform infrared (FTIR) spectrum and the corresponding equilibrium constant are obtained. The above results indicate that the novel approach provides a chance to get new insight into various intermolecular interactions studied by spectroscopy.

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Ab initio molecular orbital and density functional study of the C6H6⋅I2 complex in the ground and excited electronic states

Abstract: The structure and energetics of the C H и I complex have been studied 6 6 2 1 1.55 eV difference between the vertical and adiabatic excitation energies of 4 AЈ and the dramatic geometry change in the CT state.

Cited by 18 publications

References 48 publications

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

Magnitude and Directionality of Halogen Bond of Benzene with C₆F₅X, C₆H₅X, and CF₃X (X = I, Br, Cl, and F)

Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching

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Ab initio molecular orbital and density functional study of the C6H6⋅I2 complex in the ground and excited electronic states

Abstract: The structure and energetics of the C H и I complex have been studied 6 6 2 1 1.55 eV difference between the vertical and adiabatic excitation energies of 4 AЈ and the dramatic geometry change in the CT state.

Cited by 18 publications

References 48 publications

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

Electron-Rich Sites at the Surface of Periodic Mesoporous Organosilicas: A UV−Visible Characterization of Adsorbed Iodine

Magnitude and Directionality of Halogen Bond of Benzene with C6F5X, C6H5X, and CF3X (X = I, Br, Cl, and F)

Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching

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Magnitude and Directionality of Halogen Bond of Benzene with C₆F₅X, C₆H₅X, and CF₃X (X = I, Br, Cl, and F)