Induced-fit expansion and contraction of a self-assembled nanocube finely responding to neutral and anionic guests

Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond to the shape and electrostatic surfaces of guest molecules. Here we report a water-soluble artificial molecular host that can sensitively respond to the size, shape, and charged state of guest molecules. The molecular host, i.e. nanocube, is an assembled structure consisting of six gear-shaped amphiphiles (GSAs). This nanocube can expand or contract its size upon the encapsulation of neutral and anionic guest molecules with a volume ranging from 74 to 535 Å3 by induced-fit. The responding property of this nanocube, reminiscent of a feature of biological molecules, arises from the fact that the GSAs in the nanocubes are connected to each other only through the hydrophobic effect and very weak intermolecular interactions such as van der Waals and cation-π interactions

Induced-fit expansion and contraction of a self-assembled nanocube finely responding to neutral and anionic guests

Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond to the shape and electrostatic surfaces of guest molecules. Here we report a water-soluble artificial molecular host that can sensitively respond to the size, shape, and charged state of guest molecules. The molecular host, i.e. nanocube, is an assembled structure consisting of six gear-shaped amphiphiles (GSAs). This nanocube can expand or contract its size upon the encapsulation of neutral and anionic guest molecules with a volume ranging from 74 to 535 Å3 by induced-fit. The responding property of this nanocube, reminiscent of a feature of biological molecules, arises from the fact that the GSAs in the nanocubes are connected to each other only through the hydrophobic effect and very weak intermolecular interactions such as van der Waals and cation-π interactions.UTokyo FOCUS Press releases掲載「取り込む分子の大きさ・形・電荷に応答して膨らんだり縮んだりする分子カプセル」＜研究成果＞ URI: https://www.u-tokyo.ac.jp/focus/ja/press/z0109_00048.htmlUTokyo FOCUS Press releases "Don’t underestimate the Force Researchers discover weak chemical interactions hold together box of infinite possibilities" URI: https://www.u-tokyo.ac.jp/focus/en/press/z0508_00014.htm

Supramolecular Assemblies of Dipyrrolyldiketone Cu^II Complexes

Dipyrrolyldiketones are essential building units of anion-responsive π-electronic molecules and ion-pairing assemblies. Here, we demonstrated that they form complexes with CuII characterized by planar geometries. The solid-state stacking assembled structures, as revealed by single-crystal X-ray analysis, were modulated by the substitution of pyrrole units. The rectangular shapes of the CuII complexes resulted in the formation of mesophases upon introduction of aliphatic chains

Supramolecular Assemblies of Dipyrrolyldiketone CuII Complexes

Dipyrrolyldiketones are essential building units of anion-responsive π-electronic molecules and ion-pairing assemblies. Here, we demonstrated that they form complexes with CuII characterized by planar geometries. The solid-state stacking assembled structures, as revealed by single-crystal X-ray analysis, were modulated by the substitution of pyrrole units. The rectangular shapes of the CuII complexes resulted in the formation of mesophases upon introduction of aliphatic chains

Ion-pairing assemblies of π-extended anion-responsive organoplatinum complexes

ABSTRACTPtII complexes of π-extended dipyrrolyldiketones were synthesized as anion-responsive π-electronic molecules. The dipyrrolyldiketone PtII complexes exhibited red-shifted absorption and photoluminescence properties. In the solid state, [1 + 1]-type anion complexes formed charge-by-charge ion-pairing assemblies when combined with countercations. Detailed theoretical studies of the packing structures revealed favorable interactions between the planar anion complexes and π-electronic cations

Cyclic Anion-Responsive π‑Electronic Molecules That Overcome Energy Losses Induced by Conformation Changes

Preorganized structures suitable for anion binding were prepared by introducing dipyrrolyldiketone BF₂ complexes as acyclic anion-responsive π-electronic molecules into macrocycles. Pyrrole-inverted conformations, which typically present low stability in the case of acyclic derivatives, were obtained by covalent linkages through ring-closing olefin metathesis, exhibiting extremely high affinity for different anions

Liquid Crystals Comprising π-Electronic Ions from Porphyrin–AuIII Complexes

Summary: Porphyrin–AuIII complexes were found to act as π-electronic cations, which can combine with various counteranions, including π-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin–AuIII complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotropic liquid crystals, whose ionic components were highly organized by π–π stacking and electrostatic interactions. : Chemistry; Supramolecular Chemistry; Electronic Materials Subject Areas: Chemistry, Supramolecular Chemistry, Electronic Material