Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2′-Bi-1H-imidazole System. II. Crystal Structures and Charge-Transfer Complex Formations

Studies of the crystal structures and formation of a charge-transfer (CT) complex proved that 2,2′-bi-1H-imidazole (H2BIM0) forms a new system concerned with the interplay of proton-transfer (PT) and electron-transfer (or charge-transfer (CT)) interactions. X-Ray crystal analyses of newly isolated species, 2-(2-1H-imidazolyl)-1H-imidazolium (H3BIM+) and 2,2′-bi-1H-imidazolium (H4BIM2+), revealed the formation of strong hydrogen bonds along the side-by-side direction of the molecular plane. CT complexes of H3BIM+ and H4BIM2+ with the 7,7,8,8-tetracyanoquinodimethane derivatives (TCNQs) were synthesized by a method metathesis, and the crystal structure of (H3BIM+)2(TCNQ−)2(TCNQ0) was determined. During CT complex formation, the initial simple protonated states of [H3BIM+] or [H4BIM2+] changed to different ones, for example, [H4BIM2+]x[H3BIM+]1−x, [H3BIM+]x[H2BIM0]1−x, and H2BIM0. According to the protonated states of the H2BIM system, the formal charge of the TCNQs in the CT complexes varies from completely...

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