Allyl vs ethyl substituted thioquinoline complexes with diiodine: Halogen bonds and iodocyclization

Matveychuk, Yury V.; Ilkaeva, Marina; Вершинина, Е. А.; Batalov, V. I.; Morozov, Roman; Барташевич, Е. В.

doi:10.1016/j.molstruc.2016.04.072

Cited by 16 publications

(5 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…13 The absorption characterized here is assigned to the SOMO-2 to SOMO, π→σ*, that differs from the older literature that excluded this assignment based on the symmetry forbidden nature of the transition that is not relevant to the bismuth diiodide adduct. 13 A TD-DFT analysis of diiodide using multiple functionals and basis sets (B3LYP/aug-cc-pVTZ and PBE0/6-311g** (d,p)), used previously for accurate iodine calculations, 14,15 supports the assignment of 600−800 nm band as a π→σ* transition (Table S1). The ∼640 nm absorption transient is assigned to an η 2 ligated I 2…”

Section: •−mentioning

confidence: 77%

Light Excitation of a Bismuth Iodide Complex Initiates I–I Bond Formation Reactions of Relevance to Solar Energy Conversion

Maurer

Meyer

2017

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The titration of iodide into acetonitrile solutions of BiI resulted in the formation of [BiI]. Ligand-to-metal charge transfer (LMCT) excitation of [BiI] yielded a transient species assigned as the diiodide anion I directly ligated to Bi, [Bi(I)I]. With 20 ns time resolution, transient absorption measurements revealed the appearance of two species assigned on the analysis of the iodine molecular orbitals as an η ligated I, [(η-I)BiI] (λ = 640 nm), and an η species [(η-I)BiI] (λ = 750 nm). The rapid appearance of this intermediate was attributed to intramolecular I-I bond formation. The [(η-I)BiI] subsequently reacted with 1 equiv of iodide to yield [(η-I)BiI]. Interestingly, [(η-I)BiI] decayed to ground state products with a first-order rate constant of k = 2 × 10 s. Under the same experimental conditions, I in CHCN rapidly disproportionates with a tremendous loss of free energy, ΔG = -2.6 eV. The finding that metal ligation inhibits this energy wasting reaction is of direct relevance to solar energy conversion. The photochemistry itself provides a rare example of one electron oxidized halide species coordinated to a metal ion of possible relevance to reductive elimination/oxidation addition reaction chemistry of transition metal catalysts.

show abstract

Section: •−mentioning

confidence: 77%

Light Excitation of a Bismuth Iodide Complex Initiates I–I Bond Formation Reactions of Relevance to Solar Energy Conversion

Maurer

Meyer

2017

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Because of the complexity of iodine chemistry, it is difficult to study it thoroughly by experimental methods, such as UV–vis spectro-photometry, ,, Raman spectroscopy, infrared spectroscopy, and X-ray diffraction. With the progress of computer science, quantum chemistry calculation has been extensively used to study chemical structures, physical properties, and reaction mechanisms. − For example, a deep understanding of the halogen bond has been obtained with the aid of quantum chemistry calculations. − The term “halogen bonding” is usually taken to mean the noncovalent interaction of a halogen atom X (Cl, Br, I) in one molecule with a negative site, such as the lone pair electrons (LPE) of a Lewis base, in another. , It can be related to the presence of a region of positive electrostatic potential, the σ-hole, on the outermost portion of the halogen atom surface. , Thus, a halogen bond is often present between a halogen atom (Cl, Br, I) and an atom containing a lone pair of electrons (O, N, S, Cl, Br, I...).…”

Section: Introductionmentioning

confidence: 99%

Investigating the Complexation and Release Behaviors of Iodine in Poly(vinylpyrrolidone)-Iodine Systems through Experimental and Computational Approaches

Guan

2020

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Poly(vinylpyrrolidone)-iodine (PVPI)-based materials have attracted significant attention, owing to their effective inhibition of COVID-19. However, the complexation and release manner of iodine in PVPI are not fully understood. This article reveals the role of halogen bonding in PVPI chemistry through a combination of experimental and computational approaches, including ultraviolet−visible spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, electronic structure calculations, electronically excited-state analysis, electrostatic potential mapping on molecular van der Waals surfaces, halogen bond energy calculations, and thermodynamic equilibrium analysis. Our research shows that, in both the solid state and solution, PVPI contains iodine molecules bonded with carbonyl groups as well as polyiodides derived from the ionization and assembling of iodine molecules. The iodophors (i.e., PVP, iodide, and polyiodides) interact with iodine molecules through halogen bonds. The halogen bond energy is as low as 2−8 kcal/mol, enabling the easy release of iodine by the iodophors. In PVPI solutions, the complexation and release of iodine reach a chemical equilibrium that is susceptible to temperature and other iodophors. Raising the temperature favors the release of iodine. Some synthetic polymers, biological proteins, and phospholipids can extract iodine molecules from solutions of PVPI, demonstrating good iodophor abilities.

show abstract

“…Despite these inspiringb eginning, our attemptst ot race any consequent researchi nt his field were not successful. Considering that the chemistry of polyhalides has experienced ar enaissance within the last few years (a numbero ff undamentally important results were reported), [27][28][29][30][31][32][33][34][35][36][37] we believe that these studies are worth resuming and pursuingf urther,b yu sing the panoply of modern methods and approaches.…”

Section: Introductionmentioning

confidence: 99%

Bromo‐ and Polybromoantimonates(V): Structural and Theoretical Studies of Hybrid Halogen‐Rich Halometalate Frameworks

Adonin

Bondarenko

Abramov

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

Cation-dependent reactions "[SbBr ] +Br +HBr+CationBr " result in the formation of bromide/polybromide complexes with zero-, one-, two-, or three-dimensional supramolecular frameworks and different Br/Sb ratios (up to 11). Seven new compounds representing six structural types were characterized by XRD and thermogravimetric analysis and DFT calculations enabled estimation of the energies of the Br⋅⋅⋅Br contacts (1.1-4.6 kcal mol ).

show abstract

Allyl vs ethyl substituted thioquinoline complexes with diiodine: Halogen bonds and iodocyclization

Cited by 16 publications

References 31 publications

Light Excitation of a Bismuth Iodide Complex Initiates I–I Bond Formation Reactions of Relevance to Solar Energy Conversion

Light Excitation of a Bismuth Iodide Complex Initiates I–I Bond Formation Reactions of Relevance to Solar Energy Conversion

Investigating the Complexation and Release Behaviors of Iodine in Poly(vinylpyrrolidone)-Iodine Systems through Experimental and Computational Approaches

Bromo‐ and Polybromoantimonates(V): Structural and Theoretical Studies of Hybrid Halogen‐Rich Halometalate Frameworks

Contact Info

Product

Resources

About