Thermally switchable polyrotaxane as a model of stimuli-responsive supramolecules for nano-scale devices

A polyrotaxane consisting of many β-cyclodextrins (β-CDs) and a triblock copolymer of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) capped with bulky end-groups was synthesized as a model of stimuli-responsive supramolecules for nanoscale devices. The polyrotaxane was reversibly soluble-insoluble in water in response to temperature. This was achieved through the assembled and dispersed states of β-CDs along the block copolymer. It is considered that intermolecular hydrogen bondings of β-CDs, as well as the PEG segment length of the copoloymer, are predominant factors for regulating such thermally switchable behavior of the polyrotaxane.     

Noncovalent Modification of Cycloparaphenylene by Catenane Formation Using an Active Metal Template Strategy**

The active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π-conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π-conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application. However, most CPP modifications require early stage functionalization and the direct modification of CPPs is very limited. Herein, we report the synthesis of a catenane consisting of [9]CPP and a 2,2′-bipyridine macrocycle as a new CPP analogue that contains a reliable synthetic scaffold enabling diverse and concise post-modification. Following the AMT strategy, the [9]CPP-bipyridine catenane was successfully synthesized through Ni-mediated aryl-aryl coupling. Catalytic C−H borylation/cross-coupling and metal complexation of the bipyridine macrocycle moiety, an effective post-functionalization method, were also demonstrated with the [9]CPP-bipyridine catenane. Single-crystal X-ray structural analysis revealed that the [9]CPP-bipyridine catenane forms a tridentated complex with an Ag ion inside the CPP ring. This interaction significantly enhances the phosphorescence lifetime through improved intermolecular interactions.     

Supramolecular network formation through inclusion complexation of an α‐cyclodextrin‐based molecular tube

The supramolecular network formation through inclusion complexation between α‐cyclodextrin‐based molecular tube (MT) and poly(ethylene oxide) monocetylether‐graft‐dextran (5C₁₆PEO‐g‐Dex40) was demonstrated. From isothermal titration calorimetric (ITC) measurement, it was confirmed that MT formed an inclusion complex with two C₁₆PEO side chains in 5C₁₆PEO‐g‐Dex40. From viscosity measurements, the specific viscosity of the solution containing MT and 5C₁₆PEO‐g‐Dex40 was much larger than that containing 5C₁₆PEO‐g‐Dex40. It is considered that MT participates in the supramolecular network formation of 5C₁₆PEO‐g‐Dex40 through inclusion complexation with two C₁₆PEOs grafted to independent Dex40s.