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Dynamic M/P invertible helicity was successfully induced at a SiO2 surface immobilized with a dynamic helical trinuclear cobalt complex, [LCo3(NHMe2)6](OTf)3, using chiral ((R) or (S))-1-phenylethylamine. Solid-state CD spectra and theoretical calculations suggested that the fixation of the M/P helical complex on the surface via coordination interactions was the key factor of the induced chirality at the surface. [ABSTRACT FROM AUTHOR]

Unique bench‐stable rhodium(I) complexes bearing an aryl‐substituted 1,3,5‐hexatriene chain have been synthesized by reactions of (bicyclo[2.2.1]hepta‐2,5‐diene)rhodium(I) chloride dimer ([Rh(nbd)Cl]2) with aryl boronic acids and diphenylacetylenes in the presence of a 50 % aqueous solution of KOH. X‐ray crystallographic analysis of the isolated complexes indicated a square‐planar structure stabilized by a strong interaction with one of the aryl groups on the 1,3,5‐hexatriene chain, which has a helical structure. The helical chirality of the isolated rhodium complexes was confirmed to be sufficiently stable to be resolved into enantiomers by HPLC on a chiral stationary phase at room temperature. It was confirmed that the isolated rhodium complexes functioned as initiators for living polymerization of phenylacetylene to give cis‐stereoregular poly(phenylacetylene) with a well‐controlled molecular weight. [ABSTRACT FROM AUTHOR]

We developed a new strategy, ligand exchange strategy, for tuning the response speeds of helicity inversion of a metal‐containing helical structure. This is based on the exchange of the two axial amine ligands of the octahedral Co3+ centers in the metallocryptands [LCo3X6] (X=axial amine ligand). The response speeds of the helicity induction were controlled by using different combinations of achiral and chiral amines as the starting and entering ligands, respectively. The response speeds of the helicity inversion from P to M were also tuned by using different combinations of chiral amines. The response speeds of helicity inversion were efficiently controlled by the ligand exchange strategy using a metal‐containing helical structure. The ligand exchange between different kinds of achiral and chiral amines as the starting and entering ligands resulted in a variation of the response speeds both in the helicity induction and helicity inversion. [ABSTRACT FROM AUTHOR]

Dynamic M/P invertible helicity was successfully induced at a SiO2 surface immobilized with a dynamic helical trinuclear cobalt complex, [LCo3(NHMe2)6](OTf)3, using chiral ((R) or (S))-1-phenylethylamine. Solid-state CD spectra and theoretical calculations suggested that the fixation of the M/P helical complex on the surface via coordination interactions was the key factor of the induced chirality at the surface. [ABSTRACT FROM AUTHOR]