Water-Mediated Reversible Control of Three-State Double-Stranded Titanium(Ⅳ) Helicates

摘要

A stimuli-responsible reversible structural transformation is of key importance in biological systems. We now report a unique water-mediated reversible transformation among three discrete double-stranded dinuclear titanium(Ⅳ) achiral meso- and chiral rac-helicates linked by a mono(μ-oxo) or a bis(μ-hydroxo) bridge between the titanium ions through hydration/dehydration or its combination with a water-mediated dynamic cleavage/re-formation of the titanium-phenoxide (Ti-OPh) bonds. The bis(μ-hydroxo) bridged titanium(Ⅳ) meso-helicate prepared from two tetraphenol strands with titanium(Ⅳ) oxide was readily dehydrated in CD_3CN containing a small amount of water upon heating, accompanied by Ti-OPh bond cleavage/re-formation catalyzed by water, resulting in the formation of the mono(μ-oxo)-bridged rac-helicate, which reverted back to the original bis(μ-hydroxo)-bridged meso-helicate upon hydration in aqueous CD_3CN. These reversible transformations between the meso- and rac-helicates were also promoted in the presence of a catalytic amount of an acid, which remarkably accelerated the reactions at lower temperature. Interestingly, in anhydrous CD_3CN, the bis(μ-hydroxo)-bridged meso-helicate was further slowly converted to a different helicate, while its meso-helicate framework was maintained, namely the mono(μ-oxo)-bridged meso-helicate, through dehydration upon heating and its meso to meso transformation was significantly accelerated in the presence of cryptand[2.2.1], which contributes to removing Na~+ ions coordinated to the helicate. Upon cooling, the backward meso to meso transformation took place via hydration. Hence, three different, discrete double-stranded chiral rac- and achiral meso-titanium(Ⅳ) helicates linked by a mono(μ-oxo) or a bis(μ-hydroxo) bridge were successfully generated in a controllable manner by a change in the water content of the reaction media.