Conformation and Visual Distinctionbetween Urea and ThioureaDerivatives by an Acetate Ion and a Hexafluorosilicate Cocrystal ofthe Urea Derivative in the Detection of Water in Dimethylsulfoxide

摘要

Structures of different solvates and solute–solvent interactions of 4-(3-(4-nitrophenyl)urido)benzoate (>L>1) and methyl-4-(3-(4-nitrophenyl)thiourido)benzoate (>L>2) with different solvents are analyzed. The solution of >L>1 with tetrabutylammonium acetate (TBAA) in dimethylsulfoxide (DMSO) is colorless, but a similar solution of >L>2 with TBAA is orange. On the other hand, respective solutions of these urea and thiourea derivatives with tetrabutylammonium fluoride (TBAF) in DMSO are orange. Urea derivative >L>1 facilitates the reaction of TBAF with glass to form tetrabutylammonium hexafluorosilicate, which on further interaction with >L>1 forms cocrystal 2>L>1·(TBA)2SiF6. Reorganization of hydrogen-bonded self-assembly of 2>L>1·(TBA)2SiF6 in DMSO caused by water is established by a dynamic light scattering study. With an increase in the amount of water in the solution, visual color changes from orange to colorless, and the color changes are reversed upon the addition of a dehydrating agent such as molecular sieves. Solvates of >L>1 with DMSO, dimethylformamide (DMF), and dimethylacetamide are quasi-isostructural. The respective self-assembly of these solvatesdiffers due to orientations of aromatic rings and the carbomethoxygroup across the thioamide/amide bond. Significant differences inself-assemblies of the respective DMSO solvate of >L>1 and >L>2 areobserved; self-assembly of the former has dimeric subassemblies asrepeat units, whereas the latter has monomeric subassemblies. DMFsolvates of >L>1 and dimethylacetamideof >L_>1 are built by dimeric subassembliesto form self-assembled structures, but these subassemblies differin the orientation of the carbomethoxy group across the urea units.