The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a selfassembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the selfassembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.

A graphdiyne analogue featuring pyrazine as the aromatic center was synthesized under air using a liquid/liquid interfacial synthesis. It served as a metal-free electrocatalyst for the hydrogen evolution reaction (HER) from water.

Of a variety of intercalated materials, 2D intercalated systems have attracted much attention both as materials per se, and as a platform to study atoms and molecules confined among nanometric layers. High‐precision fabrication of such structures has, however, been a difficult task using the conventional top‐down and bottom‐up approaches. The de novo synthesis of a 3‐nm‐thick nanofilm intercalating a hydrogen‐bonded network between two layers of fullerene molecules is reported here. The two‐layered film can be further laminated into a multiply film either in situ or by sequential lamination. The 3 nm film forms uniformly over an area of several tens of cm2 at an air/water interface and can be transferred to either flat or perforated substrates. A free‐standing film in air prepared by transfer to a gold comb electrode shows proton conductivity up to 1.4 × 10−4 S cm−1. Electron‐dose‐dependent reversible bending of a free‐standing 6‐nm‐thick nanofilm hung in a vacuum is observed under electron beam irradiation.

Organofullerene amphiphiles show diverse behaviors in water, forming vesicles, micelles, Langmuir–Blodgett films, and anisotropic nanostructures. We found that gradual in situ protonation of an organic solution of (4-heptylphenyl)5C60 –K+ by water or buffer generates the corresponding protonated molecule, (4-heptylphenyl)5C60H, which self-assembles to form nano- and microspheres of organofullerene (fullerspheres) with uniform diameters ranging from 30 nm to 2.5 μm that are controlled by the preparation or pH of the buffer. By using an aqueous solution of an organic dye, inorganic nanoparticle, protein, and virus, we encapsulated these entities in the fullersphere. This approach via self-assembly is distinct from other preparations of organic core–shell particles that generally require polymerization for the construction of a robust shell. The sphere is entirely amorphous, thermally stable up to 300 °C under vacuum, and resistant to electron irradiation, and we found the unconventional utility of the sphere for electron tomographic imaging of nanoparticles and biomaterials.