Controllable and Diversiform Topological Morphologies of Self‐Assembling Supra‐Amphiphiles with Aggregation‐Induced Emission Characteristics for Mimicking Light‐Harvesting Antenna

Abstract

Controllable construction of diversiform topological morphologies through supramolecular self-assembly on the basis of single building block is of vital importance, but still remains a big challenge. Herein, a bola-type supra-amphiphile, namely DAdDMA@2-CD, is rationally designed and successfully prepared by typical host-guest binding-cyclodextrin units with an aggregation-induced emission (AIE)-active scaffold DAdDMA. Self-assembling investigation reveals that several morphologies of self-assembled DAdDMA@2-CD including leaf-like lamellar structure, nanoribbons, vesicles, nanofibers, helical nanofibers, and toroids, can be straightforwardly fabricated by simply manipulating the self-assembling solvent proportioning and/or temperature. To the best of knowledge, this presented protocol probably holds the most types of self-assembling morphology alterations using a single entity. Moreover, the developed leaf-like lamellar structure performs well in mimicking the light-harvesting antenna system by incorporating with a Förster resonance energy transfer acceptor, providing up to 94.2% of energy transfer efficiency.

Artificial Light‐Harvesting Systems Based on AIEgen‐branched Rotaxane Dendrimers for Efficient Photocatalysis

“…Meanwhile,t he signals of the methylene protons near the platinum-acetylide moiety (H 3-7 )underwent the obvious upfield shifts (Figure 3a). Such interesting solvent-induced motions of the wheel component of the [2]rotaxane was possibly due to the breaking of the hydrogen bonding between the pillar [5]arene ring and the urea moiety that led to the translational motion of the pillar [5]arene ring, which was in accord with our previous reports on solventinduced switching of similar rotaxanes. [13b,d] To confirm such hypothesis,the model [2]rotaxane TPE-RC without the urea moiety was synthesized (Scheme S9).…”

“…In this study,an ew TPE-functionalized [2]rotaxane [14] TPE-R was designed as the key building block (Figure 2). In the [2]rotaxane,the pillar [5]arene macrocycle S3 functionalized with two TIPS-protected alkynes was employed as the wheel components. [15] It should be noted that the TIPSprotected alkynes could be gently converted to the alkyne group that further serves as reactive sites for dendrimer growth.…”

“…With the targeted TPE-branched rotaxane dendrimers in hand, their AIE behaviors were then evaluated. In this study, CH 2 Cl 2 was selected as the good solvent and MeOH was chosen as the poor solvent, respectively.Due to the existence of the urea moiety in each branch of these rotaxane dendrimers as the stimuli-responsive site,t he addition of MeOH was supposed to play dual roles.O no ne hand, the increase amount of MeOH could significantly change the polarity of the solvent, which might further induce the movement of the pillar [5]arene rings away from the urea moiety to the alkyl chain moiety through the interaction between the urea moiety with the MeOH molecules. [18] On the other hand, such solventinduced motions of the wheel component would further lead to the modulation of the AIE behaviors of the integrated TPEbranched rotaxane dendrimers, making them attractive as smart AIE-active macromolecules.…”

“…[4] In contrast to traditional fluorescent molecules with ACQc haracteristics,A IEgens reveal high emission in aggregated states because of the restricted intramolecular motion (RIM), thereby making them excellent candidates as donors for the construction of novel artificial LHSs. [5] Moreover, besides the choices of suitable donors,t he accurate positioning of these donors,w hich will directly influence the key energy transfer process,are also crucial for efficient light harvesting. [6] To achieve this goal, dendrimers have evolved to be privileged and most frequently used platforms for the constructions of artificial LHSs due to their unique highly branched and star-shaped feature as well as well-tuned structures for well-defined arrangements of chromophores.…”

An Artificial Light‐Harvesting System with Tunable Fluorescence Color in Aqueous Sodium Dodecyl Sulfonate Micellar Systems for Photochemical Catalysis

“…So far, many artificial light‐harvesting systems have been constructed to investigate the energy transfer process mechanism especially the fluorescence resonance energy transfer (FRET) process. [ 3‐4 ] Among them, supramolecular self‐assembly systems including surface‐cross‐linked micelles, [ 5‐7 ] supramolecular polymers, [ 8‐14 ] supramolecular coordination‐driven assemblies, [ 15‐19 ] organic nanocrystals, [ 20‐21 ] supramolecular host‐guest assemblies [ 22‐33 ] have received widespread attention due to their simple molecular design and adjustability of functional assembly, providing more opportunities for people to understand the physical process of light. Due to the convenience of construction and the avoidance of complex synthesis, the construction of a light‐harvesting system using the microenvironment provided by the micelles assembled by surfactants has attracted extensive attention.…”