Stiff-Stilbene-Bridged Biscalix[4]arene as a Highly Light-Responsive Supramolecular Gelator.

A newly designed stiff-stilbene functionalized biscalix[4]arene in its cis form Z-1 could be near-quantitatively photoswitched to the trans-isomer E-1 under irradiation of 385 nm UV light. The trans-biscalix[4]arene E-1 was found to be a supergelator in nonpolar organic solvents, e.g., cyclohexane, hexane, pentane, and ether, with critical gelation concentrations as low as 0.2, 0.5, 0.5, and 0.4% w/v, respectively. The cis-trans configurational isomerism of biscalix[4]arene 1 resulted in distinct self-assembly modes, leading to interesting microscopic morphological changes from honeycomb and ringlike structures to rodlike dense fibrous networks.

Controlled Sol-Gel and Diversiform Nanostructure Transitions by Photoresponsive Molecular Switching of Tetraphenylethene- and Azobenzene-Functionalized Organogelators.

The implementation of stimuli-responsive materials with dynamically controllable features has long been an important objective that challenges chemists in the materials science field. We report here the synthesis and characterization of [2]rotaxanes (R1 and R1-b) with a molecular shuttle and photoresponsive properties. Axles T1 and T1-b were found to be highly efficient and versatile organogelators toward various nonpolar organic solvents, especially p-xylene, with critical gelation concentrations as low as 0.67 and 0.38 w/v %, respectively. The two molecular stations of switchable [2]rotaxanes (R1 and R1-b) can be revealed or concealed by t-butylcalix[4]arene macrocycle, thus inhibiting the gelation processes of the respective axles T1 and T1-b through the control of intermolecular hydrogen-bonding interactions. The sol-gel transition of axles T1 and T1-b could be achieved by the irradiation of UV-visible light, which interconverted between the extended and contracted forms. Interestingly, the morphologies of organogels in p-xylene, including flakes, nanobelts, fibers, and vesicles depending on the molecular structures of axles T1 and T1-b, were induced by UV-visible light irradiation. Further studies revealed that acid-base-controllable and reversible self-assembled nanostructures of these axle molecules were mainly constructed by the interplay of multi-noncovalent interactions, such as intermolecular π-π stacking, CH-π, and intermolecular hydrogen-bonding interactions. Surprisingly, our TPE molecular systems (R1, R1-b, T1, and T1-b) are nonemissive in their aggregated states, suggesting that not only fluorescence resonance energy transfer but also aggregation-caused quenching may have been functioning. Finally, the mechanical strength of these organogels in various solvents was monitored by rheological experiments.

Diversiform Nanostructures Constructed from Tetraphenylethene and Pyrene-Based Acid/Base Controllable Molecular Switching Amphiphilic [2]Rotaxanes with Tunable Aggregation-Induced Static Excimers.

Dual-emissive tetraphenylethene (TPE) and pyrene-containing amphiphilic molecules are of great interest because they can be integrated to form stimuli responsive materials with various biological applications. Herein, we report the study of mechanically interlocked molecules (MIMs) with aggregation-induced static excimer emission (AISEE) property through a series of TPE and pyrene-based amphiphilic [2]rotaxanes, where t-butylcalix[4]arene with hydrophobic nature was used as the macrocycle. Evidently, by adorning TPE and pyrene units in [2]rotaxanes P1, P2, P1-b, and P2-b, they display remarkable emission bands in 70% of water fraction (fw) in tetrahydrofuran (THF)/water mixture, which could be attributed to the restricted intramolecular rotation of phenyl groups, whereas prominent blue-shifted excimer emission of pyrene started to appear as fw reached 80% for P1 and 90% for P1-b, P2, and P2-b, which was ascribed to the favorable π-π stacking and hydrophobic interactions of the pyrene rings that enabled their static excimer formation. The well-defined distinct amphiphilic nanostructures of [2]rotaxanes including hollowspheres, mesoporous nanostructures, spheres, and network linkages can be driven smoothly depending on the molecular structures and their aggregated states in THF/water mixture. These fascinating diversiform nanostructures were mainly controlled by the skillful manner of reversible molecular shuttling of t-butylcalix[4]arene macrocycle and also the interplay of multinoncovalent interactions. To further understand the aggregation capabilities of [2]rotaxanes, the human lung fibroblasts (MRC-5) living cell incubated with either P1, P2, P1-b, or P2-b was studied and monitored by confocal laser scanning microscopy. The AISEE property was achieved at an astonishing level by integrating TPE and pyrene to MIM-based reversible molecular switching [2]rotaxanes; furthermore, distinct nanostructures, especially hollowspheres and mesoporous nanostructures, were observed, which are rarely reported in the literature but are highly desirable for future applications.

Exploration of Energy Modulations in Novel RhB-TPE-Based Bichromophoric Materials via Interactions of Cu(2+) Ion under Various Semiaqueous and Micellar Conditions.

Novel bichromophoric materials TR-A and TR-B consisting of an entirely new combination of TPE and RhB units were developed to explore the optimum conditions of energy modulations via pH variation and Cu(2+) interaction at various water contents of CH3CN. Interestingly, TR-A and TR-B, at 60 and 70% water contents, respectively, favored the optimum Cu(2+)-mediated energy modulations from TPE to RhB and thus achieve the brightest orange emissions of free RhB with complete disappearance of aggregation-induced emission (AIE) from TPE. Furthermore, various micellar conditions of triton-X-100, SDS, and CTAB were employed to adjust energy modulations of TR-A and TR-B at high water contents (at 80 and 90%, respectively). The incorporation of RhB into triton-X-100 micellar cavities disrupted AIE from TPE; thus, none of the energy modulations from TPE to RhB occurred even in the presence of Cu(2+) ion. Interestingly, the micellar conditions of anionic surfactant (SDS) favored the increased local concentration of Cu(2+) ions in the vicinity of scavangable RhB and facilitated the generation of noncyclic free RhB in situ via bright-orange emissions.

Acid/Base and H2PO4(-) Controllable High-Contrast Optical Molecular Switches with a Novel BODIPY Functionalized [2]Rotaxane.

A novel multifunctional mechanically interlocked switchable [2]rotaxane R4 containing two molecular stations and rotaxane arms terminated with boron-dipyrromethene (BODIPY) fluorophores and its derivatives were synthesized for the first time by CuAAC click reaction. The shuttling motion of macrocycle between the dibenzylammonium and triazolium recognition sites and the distance dependent photoinduced electron transfer process of R4 is demonstrated by utilizing external chemical stimuli (acid/base). Interestingly, the reversible self-assembly process of R4 was recognized by the acid-base molecular switch strategy. Notably, two symmetrical triazolium groups acted as molecular stations, H2PO4(-) receptors, and H-bonded donors. Both [2]rotaxane R4 and thread R2 demonstrated excellent optical responses and high selectivity toward H2PO4(-) ion. The specific motion and guest-host interactions of mechanically interlocked machines (MIMs) were also further explored by quantum mechanical calculations. The thread R2 also demonstrated to enable the detection of H2PO4(-) in RAW 264.7 cells successfully.