Soichiro Ogi

The mechanism of supramolecular polymerization has been elucidated for an archetype organogelator molecule composed of a perylene bisimide aromatic scaffold and two amide substituents. This molecule self-assembles into elongated one-dimensional nanofibers through a cooperative nucleation-growth process. Thermodynamic and kinetic analyses have been applied to discover conditions (temperature, solvent, concentration) where the spontaneous nucleation can be retarded by trapping of the monomers in a

We have investigated the kinetic and thermodynamic supramolecular polymerizations of a series of amide-functionalized perylene bisimide (PBI) organogelator molecules bearing alkyl spacers of varied lengths (ethylene to pentylene chains, PBI-1-C2 to PBI-1-C5) between the amide and PBI imide groups. These amide-functionalized PBIs form one-dimensional fibrous nanostructures as the thermodynamically favored states in solvents of low polarity. Our in-depth studies revealed, however, that the kinetic

Far-from-equilibrium thermodynamic systems that are established as a consequence of coupled equilibria are the origin of the complex behavior of biological systems. Therefore, research in supramolecular chemistry has recently been shifting emphasis from a thermodynamic standpoint to a kinetic one; however, control over the complex kinetic processes is still in its infancy. Herein, we report our attempt to control the time evolution of supramolecular assembly in a process in which the supramolecu

Amino acid based diamides are widely used as a substructure in supramolecular polymers and are also key components of polypeptides that help to understand protein folding. The interplay of folding and aggregation of a diamide was used to achieve seed-initiated supramolecular polymerization. For that purpose, a pyrene-substituted diamide was synthesized in which pyrene is used as a tracer to monitor the supramolecular polymerization. Thermodynamics and time-dependent studies revealed that the fol

Whilst bacteriochlorophyll <i>c</i>, <i>d</i>, and <i>e</i> dyes self-assemble into the most efficient light harvesting J-aggregate systems found in nature, their supramolecular packing arrangements are still a matter of debate and a significant number of models have been suggested for their local and long-range ordering. Here we reveal for a synthetic model system based on a zinc chlorin (ZnChl) dye an intriguing interplay of two competing aggregation pathways by kinetic and thermodynamic studi

We report the kinetically controlled supramolecular polymerization of boron-containing π-conjugated molecules, which was enabled by a seeding method based on dual trapping of a metastable state by synergistic intramolecular hydrogen bonding and Lewis acid-based complexation. Planarized triarylborane-based <b>1</b>, which bears a diamide chain with chiral alkyl groups, was synthesized. Upon cooling, the solution of monomer <b>1</b> afforded a supramolecular polymerization in a cooperative manner

Supramolecular rotor: The interlocking of two porphyrin-based molecular rotors into a bevel-gear-shaped structure is demonstrated (see figure). The mechanical interactions between the teeth of the two porphyrin rotors enabled them to mesh and rotate with almost identical activation energies. Switching the rotational activities of one rotor by using chemical stimulation induced a change in the cooperative rotational motions of both rotors.

We report the thermodynamic and kinetic aqueous self-assembly of a series of amide-functionalized dithienyldiketopyrrolopyrroles (TDPPs) that bear various hydrophilic oligoethylene glycol (OEG) and hydrophobic alkyl chains. Spectroscopic and microscopic studies showed that the TDPP-based amphiphiles with an octyl group form sheet-like aggregates with J-type exciton coupling. The effect of the alkyl chains on the aggregated structure and the internal molecular orientation was examined via computa

Abstract Far‐from‐equilibrium thermodynamic systems that are established as a consequence of coupled equilibria are the origin of the complex behavior of biological systems. Therefore, research in supramolecular chemistry has recently been shifting emphasis from a thermodynamic standpoint to a kinetic one; however, control over the complex kinetic processes is still in its infancy. Herein, we report our attempt to control the time evolution of supramolecular assembly in a process in which the su

The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the p

Abstract Amino acid based diamides are widely used as a substructure in supramolecular polymers and are also key components of polypeptides that help to understand protein folding. The interplay of folding and aggregation of a diamide was used to achieve seed‐initiated supramolecular polymerization. For that purpose, a pyrene‐substituted diamide was synthesized in which pyrene is used as a tracer to monitor the supramolecular polymerization. Thermodynamics and time‐dependent studies revealed tha

Abstract We report here the synthesis of a light-harvesting molecule 1, in which 5,5′-diphenyl-2,2′-bithiophene units (energy donors) and a doubly strapped porphyrin (energy acceptor) are three-dimensionally connected through four alkyl chains to form a “universal joint”-like architecture. From the results of the optical properties of 1 in solution, fluorescence resonance energy transfer (FRET) takes place from the donor to the acceptor in 1 with the FRET efficiency of 99.7%. We prepared 1/polyd

Supramolecular self-assembly offers an intriguing approach to construct microarchitectures, which combine properties of their molecular constituents with dynamic supramolecular features. Control over intermolecular interactions and their resulting properties can sometimes be achieved by targeted design. However, it is often unfeasible to transfer the insights gained from a specific supramolecular synthon to another chromophore without tedious synthetic work guided by trial and error. Herein we d

For the creation of next-generation organic electronic materials, the integration of π-systems has recently become a central theme. Such functional materials can be assembled by supramolecular polymerization when aromatic π-systems are used as monomers, and the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers. Here, we demonstrate the construction of a supramolecular polymer consisting of an antiaromatic π-system as the monomer. An am