Crowding for Confinement: Reversible Isomerization of First-Generation Donor-Acceptor Stenhouse Adduct Derivatives in Water Modulated by Thermoresponsive Dendritic Macromolecules.

Mimicking nature, the reversible isomerization of hydrophobic dyes in aqueous solutions is appealing for bio-applications. Here, we report on the reversible isomerization of first-generation solvatochromic donor-acceptor Stenhouse adducts (DASAs) in water within dendritic matrices, realized either through the dendronization of DASAs or the incorporation of DASA pendants into dendronized copolymers. These dendritic macromolecules contain three-fold dendritic oligoethylene glycols (OEGs), which afford the macromolecules water-solubility and unprecedented thermoresponsive behavior. The thermoresponsive behavior of both dendronized DASAs and dendronized copolymers is dominated by the peripherals of dendritic OEGs. However, the hydrophilicity of the acceptor from DASA moieties also play a role in mediating their thermal phase transitions, and more importantly, tailor the hydrophobic interactions between dendritic OEGs and DASA moieties. Intriguingly, dendritic topologies contribute confinement to encapsulate the DASA moieties through crowding effects, and cooperative interactions from the crowded dendritic OEGs modulate the DASA moieties with different isomerization in aqueous media. The thermally induced collapse of dendritic OEGs, accompanied by the aggregation of dendritic macromolecules, leads to the formation of hydrophobic domains, which exert enhanced crowding effects to efficiently encapsulate the DASA moieties. Compared to the low molar mass of dendronized DASAs, thermally collapsed dendronized copolymers can efficiently retard the hydration of DASA pendants through cooperation between neighboring dendritic OEGs and afford the DASA pendants with better confined microenvironments to mediate their isomerization recovery by up to 90% from a cyclic charged (hydrophilic) state into a noncharged (hydrophobic) linear state in water. This dendritic confinement exhibits excellent fatigue resistance after several cycles of alternating photo-irradiation and thermal annealing at elevated temperatures.