The effect of reaction environment on the self-assembly process of an octahedron-shaped Pd6L8 capsule was investigated. Quantitative analysis of self-assembly process with 1H NMR spectroscopy revealed that the self-assembly pathway of the capsule was altered by solvent and a leaving ligand coordinating to the metal source, which are not the components of the final self-assembly. Solvents definitively determine the pathway of the self-assembly at a very early stage of the self-assembly. Contrary to the expectation that the weaker the coordination ability of the leaving ligand is, the faster the formation of the final assembly becomes, a leaving ligand with weak coordination ability tends to generate a kinetically trapped species to prevent the capsule formation under mild conditions.

The self-assembly process of a Pt(II)-linked hexagonal macrocycle consisting of six linear dinuclear Pt(II) units and six organic ditopic bent ligands was investigated. The process was monitored by 1H NMR, and the intermediates in the self-assembly were analyzed by the n–k analysis. It was found that a 1:2 complex of a dinuclear Pt(II) unit and an organic ditopic ligand was exclusively observed as an intermediate with a certain lifetime and that the reaction of the 1:2 complex is the rate-determining step in the supramolecular macrocycle formation. The key 1:2 complex was unambiguously characterized by 1H and DOSY NMR and ESI-TOF mass measurement.

An in-depth understanding of the self-assembly process at the molecular level is crucial in both biological and materials science fields. However, such research is scarce due to the difficulty in monitoring a great deal of fragmentary species that are transiently produced in the process. We present a novel method for investigating the self-assembly process of supramolecular coordination assemblies by following the time variation of the average composition of the fragmentary species, which was indirectly determined by spectroscopy. With this method, we found that the final stage is the rate-determining step of the self-assembly of an octahedron-shaped coordination capsule, and that the relative energy barrier of each step is controllable by modifying the chemical structure of the building blocks.

We report mesityllithium and p-(dimethylamino)phenyllithium as new valuable lithiating reagents, which realize Br/Li exchange reaction of bromoarenes at relatively high temperature in THF. With these reagents, we established the general and practical protocols for the selective alternate trilithiation of the hexaphenylbenzene framework.

We report a practical synthetic protocol and mechanistic details for the selective alternate derivatization of the hexaphenylbenzene (HPB) framework through a thermodynamically controlled halogen dance. The stability of the alternately trilithiated species of HPB is interpreted by the through-space interaction at the ipso-carbons of the phenyl groups of the HPB framework. By using this approach, C3-symmetric and lower-symmetric HPB derivatives possessing two or three kinds of substituents on the periphery have become easily and practically available.

Exactly six gear-shaped amphiphiles self-assemble into a highly stable, water-soluble, box-shaped capsule, in which indented hydrophobic surfaces of the components mesh with each other like gears. A water-soluble, tetrahedron-shaped capsule was also constructed from four gear-shaped amphiphiles with a template guest. These findings provide a guideline for creating aggregates with a given number of amphiphiles based on hydrophobic surface engineering.

We report mesityllithium and p-(dimethylamino)phenyllithium as new valuable lithiating reagents, which realize Br/Li exchange reaction of bromoarenes at relatively high temperature in THF. With these reagents, we established the general and practical protocols for the selective alternate trilithiation of the hexaphenylbenzene framework.

An in-depth understanding of the self-assembly process at the molecular level is crucial in both biological and materials science fields. However, such research is scarce due to the difficulty in monitoring a great deal of fragmentary species that are transiently produced in the process. We present a novel method for investigating the self-assembly process of supramolecular coordination assemblies by following the time variation of the average composition of the fragmentary species, which was indirectly determined by spectroscopy. With this method, we found that the final stage is the rate-determining step of the self-assembly of an octahedron-shaped coordination capsule, and that the relative energy barrier of each step is controllable by modifying the chemical structure of the building blocks.