Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.     

Fabrication of Self‐Oscillating Micelles with a Built‐In Oxidizing Agent

Various biological behaviors are fueled by “respiration”, which is an example of catabolism. So far, we have reported various self‐oscillating soft materials exhibiting bioinspired dynamic movements. These autonomous polymer systems are driven by the Belousov–Zhabotinsky (BZ) reaction, which is analogous to the tricarboxylic acid (TCA) cycle that is an integral part of respiration. However, in the BZ reaction, the external addition of an oxidizing agent is necessary to initiate the oxidation process, which is realized by intracellular moieties such as ubiquinone in living systems. Herein, we realized self‐oscillating micelles that are driven without the external addition of an oxidizing agent. This was achieved by embedding the oxidizing source into the structure of the self‐oscillating AB diblock copolymers. This strategy introduces a new function equivalent to intracellular oxidizing moieties, and is useful for the design of completely autonomous bioinspired materials.     

Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S₁ excited state. The S₁ planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM).     

Emission Control by Molecular Manipulation of Double‐Paddled Binuclear PtII Complexes at the Air‐Water Interface

Molecular functions depend on conformations and motions of the corresponding molecular species. An air–water interface is a suitable asymmetric field for the control of molecular conformations and motions under a small applied force. In this work, double‐paddled binuclear Pt^II complexes containing pyrazole rings linked by alkyl spacers were synthesized and their orientations and emission properties dynamically manipulated at the air–water interface. The complexes emerge from water with concurrent variation of interface orientation of the planes of the Pt^II complexes from perpendicular to parallel during mechanical compression suggesting a unique ‘submarine emission‘. Phosphorescence of the complexes is quenched at the air–water interface prior to monolayer formation with intensities subsequently rapidly increasing during monolayer compression. These results indicate that asymmetric reactions and motions might be controlled by applying mechanical force at the air–water interface.