An Experimental and Theoretical Insight into I2 /Br2 Oxidation of Bis(pyridin-2-yl)Diselane and Ditellane

Abstract

The reactivity between bis(pyridin-2-yl)diselane ^o Py₂ Se₂ and ditellane ^o Py₂ Te₂ (L1 and L2, respectively; ^o Py=pyridyn-2-yl) and I₂ /Br₂ is discussed. Single-crystal structure analysis revealed that the reaction of L1 with I₂ yielded [(HL1⁺ )(I^- )⋅5/2I₂ ]_∞ (1) in which monoprotonated cations HL1⁺ template a self-assembled infinite pseudo-cubic polyiodide 3D-network, while the reaction with Br₂ yielded the dibromide H^o PySe^II Br₂ (2). The oxidation of L2 with I₂ and Br₂ yielded the compounds H^o PyTe^II I₂ (3) and H^o PyTe^IV Br₄ (6), respectively, whose structures were elucidated by X-ray diffraction analysis. FT-Raman spectroscopy measurements are consistent with a 3c-4e description of all the X-Ch-X three-body systems (Ch=Se, Te; X=Br, I) in compounds 2, 3, H^o PyTe^II Br₂ (5), and 6. The structural and spectroscopic observations are supported by extensive theoretical calculations carried out at the DFT level that were employed to study the electronic structure of the investigated compounds, the thermodynamic aspects of their formation, and the role of noncovalent σ-hole halogen and chalcogen bonds in the X⋅⋅⋅X, X⋅⋅⋅Ch and Ch⋅⋅⋅Ch interactions evidenced structurally.

Keywords: Chalcogen Bonding; DFT; Halogen Bonding; Raman; dichalcogenide; halogen.