Multi-state photoluminescent properties of an overcrowded alkene-based molecular motor in aggregates

Photoisomerization and photoluminescence are two distinct energy dissipation path-ways in light-driven molecular motors.The photoisomerization properties of discrete molecular motors have been well established in solution,but their photoluminescent properties have been rarely reported-especially in aggregates.Here,it is shown that an overcrowded alkene-based molecular motor exhibits distinct dynamic prop-erties in solution and aggregate states,for example,gel and solid states.Despite the poor emissive properties of molecular motors in solution,a bright emission is observed in the aggregate states,including in gel and the crystalline solid.The emis-sion wavelength is highly dependent on the nature of the supramolecular packing and order in the aggregates.As a result,the fluorescent color can be readily tuned reversibly via mechanical grinding and vapor fuming,which provides a new platform for developing multi-stimuli functional materials.

Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

Supramolecular self-assembly in water based on non-covalent bonding is attracting major attention due to the potential of hydrogels and aqueous polymers in biomedical applications.Although supramolecular polymerization in organic solvents is well established,the key design features,the assembly mechanisms in water and achieving control over the aggregate structures remain challenging.Here,we present the assembly and disassembly of geometrical isomers of a stiff-stilbene bis-urea amphiphile(SA)in pure water.A remarkable feature of this system is that the(E)-isomer forms supramolecular polymers in both pure water and organic solvents.Taking advantage of this unique property,the hydrophobic effect was studied by comparing the supramolecular assembly in both systems.The assembly process inwater follows an enthalpy-driven nucleation-elongation(cooperative)supramolecular polymerization mechanism with a standard Gibbs free energy(ΔG°=−53 kJ mol^(−1))double the value of the one found in toluene.We attributed this distinctive feature to the hydrophobic effect in water.Furthermore,we discovered an isomer-dependent assembly process,which can be used to control aggregation in aqueous media.Due to the substantial geometric difference between(E)-SA and(Z)-SA,we compared their assembly in water to study the influence of different driving forces involved in the process.The supramolecular polymerization of(E)-SA was cooperatively influenced by hydrogen bonding,π-stacking,and hydrophobic effects,whereas the assembly of(Z)-SAwasmainly driven by hydrophobic effects.As a result,the fiber length of(E)-SA in water is much longer than that of(Z)-SA,presenting opportunities for geometrical control of aggregation in aqueousmedia.