Halogenated Diazabutadiene Dyes: Synthesis, Structures, Supramolecular Features, and Theoretical Studies

Abstract

Novel halogenated aromatic dichlorodiazadienes were prepared via copper-mediated oxidative coupling between the corresponding hydrazones and CCl4. These rare azo-dyes were characterized using 1H and 13C NMR techniques and X-ray diffraction analysis for five halogenated dichlorodiazadienes. Multiple non-covalent halogen···halogen interactions were detected in the solid state and studied by DFT calculations and topological analysis of the electron density distribution within the framework of Bader’s theory (QTAIM method). Theoretical studies demonstrated that non-covalent halogen···halogen interactions play crucial role in self-assembly of highly polarizable dichlorodiazadienes. Thus, halogen bonding can dictate a packing preference in the solid state for this class of dichloro-substituted heterodienes, which could be a convenient tool for a fine tuning of the properties of this novel class of dyes.

Unprecedented Coordination-Induced Bright Red Emission from Group 12 Metal-Bound Triarylazoimidazoles

“…Crystallographic parameters and refinement details for all complexes are listed in Table S1 . Overall, metrical parameters for triarylazoimidazoles in 5, 7 – 10 are similar to those reported for structurally relevant azocompounds [ 17 , 18 , 19 , 23 , 35 , 36 ] and imidazole derivatives [ 37 , 38 ]. CCDC 2058877-2058881 contain the supplementary crystallographic data for this paper.…”

Modeling of Solute-Solvent Interactions Using an External Electric Field—From Tautomeric Equilibrium in Nonpolar Solvents to the Dissociation of Alkali Metal Halides

“…Noncovalent interactions allow our world to exist. Their specific interaction energies [ 1 , 2 , 3 , 4 ], their effect on the spectral [ 5 , 6 , 7 ], chemical [ 8 , 9 ], and structural [ 10 , 11 , 12 ] properties of individual molecules, those in adducts and solutions [ 13 , 14 , 15 ], have been and remain vital to the progress of chemistry. The interpretation of spectral shifts caused by changes in the properties of a particular interaction can be carried out in sufficient detail [ 16 ].…”

Crystal structure of 2-[(E)-2-(4-bromophenyl)diazen-1-yl]-4,5-bis(4-methoxyphenyl)-1H-imidazole: the first example of a structurally characterized triarylazoimidazole

“…Numerous publications have been devoted to the development of organic crystalline materials that contain various imidazole-based architectures (Akhriff et al, 2006). Following our interest in azo dyes (Nenajdenko et al, 2020;Tskhovrebov, Vasileva et al, 2018), imidazole chemistry, imidazolylidenes and corresponding metal-carbene complexes (Tskhovrebov, Lingnau et al, 2019;Mikhaylov et al, 2018;Tskhovrebov et al, 2012), we report here the synthesis and crystal structure of (E)-2-[(4-bromophenyl)diazenyl]-4,5-bis(4-methoxyphenyl)-1H-imidazole. Although azoimidazoles form a widely studied class of azo compounds, triarylazoimidazoles have never been ISSN 2056-9890 structurally characterized.…”