Supramolecular Helical Assemblies of Dirhodium(II) Paddlewheels with 1,4-Diazabicyclo[2.2.2]octane: A Remarkable Substituent Effect on the Helical Sense Preference and Amplification of the Helical Handedness Excess of Metallo-Supramolecular Helical Polymers.

We report unique coordination-driven supramolecular helical assemblies of a series of dirhodium(II) tetracarboxylate paddlewheels bearing chiral phenyl- or methyl-substituted amide-bound m-terphenyl residues with triethylene glycol monomethyl ether (TEG) or n-dodecyl tails through a 1:1 complexation with 1,4-diazabicyclo[2.2.2]octane (DABCO). The chiral dirhodium complexes with DABCO in CHCl3/n-hexane (1:1) form one-handed helical coordination polymers with a controlled propeller chirality at the m-terphenyl groups, which are stabilized by intermolecular hydrogen-bonding networks between the adjacent amide groups at the periphery mainly via a cooperative nucleation-elongation mechanism as supported by circular dichroism (CD), vibrational CD, and variable-temperature (VT) absorption and CD analyses. The VT visible-absorption titrations revealed the temperature-dependent changes in the degree of polymerization. The columnar supramolecular helical structures were elucidated by X-ray diffraction and atomic force microscopy. The helix sense of the homopolymer carrying the bulky phenyl and n-dodecyl substituents is opposite those of other chiral homopolymers despite having the same absolute configuration at the pendants. A remarkably strong "sergeants and soldiers" (S&S) effect was observed in most of the chiral/achiral copolymers, while the copolymers of the bulky chiral phenyl-substituted dirhodium complexes with n-dodecyl chains displayed an "abnormal" S&S effect accompanied by an inversion of the helix sense, which could be switched to a "normal" S&S effect by changing the solvent composition. A nonracemic dirhodium complex of 20% enantiomeric excess bearing the less bulky chiral methyl substituents with n-dodecyl chains assembled with DABCO to form an almost one-handed helix (the "majority rule" (MR) effect), whereas the three other nonracemic copolymers showed a weak MR effect.

Remote-controlled regio- and diastereodifferentiating photodimerization of a dynamic helical peptide-bound 2-substituted anthracene.

Photodimerization of a novel 2-substituted anthracene linked to a right-handed 310-helical nonapeptide induced by long-range chiral information transfer from the remote chiral l-Val residue through a chiral domino effect proceeded in a highly regio- and diastereo-differentiating manner to produce the chiral head-to-head anti-photodimer in 90% relative yield with up to 97% diastereomeric excess.

Asymmetric Transformation Driven by Confinement and Self-Release in Single-Layered Porous Nanosheets.

Reported here is the use of single-layered, chiral porous sheets with induced pore chirality for repeatable asymmetric transformations and self-separation without the need for chiral catalysts or chiral auxiliaries. The asymmetric induction is driven by chiral fixation of absorbed achiral substrates inside the chiral pores for transformation into enantiopure products with enantioselectivities of greater than 99 % ee. When the conversion is completed, the products are spontaneously separated out of the pores, enabling the porous sheets to perform repeated cycles of converting achiral substrates into chiral products for release without compromising pore performance. Confinement of achiral substrates into two-dimensional chiral porous materials provides access to a highly efficient alternative to current asymmetric synthesis methodologies.

Enantiodifferentiating Photodimerization of a 2,6-Disubstituted Anthracene Assisted by Supramolecular Double-Helix Formation with Chiral Amines.

A novel 2,6-anthrylene-linked bis(m-terphenylcarboxylic acid) strand (1) self-associates into a racemic double-helix. In the presence of chiral mono- and diamines, either a right- or left-handed double-helix was predominantly induced by chiral amines sandwiched between the carboxylic acid strands with accompanying stacking of the two prochiral anthracene linker units in an enantiotopic face-selective way, as revealed by circular dichroism and NMR spectral analyses. The photoirradiation of the optically active double helices complexed with chiral amines proceeded in a diastereo- (anti or syn) and enantiodifferentiating way to afford the chiral anti-photodimer with up to 98 % enantiomeric excess when (R)-phenylethylamine was used as a chiral double-helix inducer. The resulting optically active anti-photodimer can recognize the chirality of amines and diastereoselectively complex with chiral amines.

Tug-of-War in a Dynamic Helical Peptide: Solvent-Induced Helix-Helix Transition of a Lactam-Bridged Peptide Composed of Point- and Axial Chiralities Remote from Each Other.

The dynamic axial chirality of oligopeptide-bound 2,2'-bipyridine (bpy) residues can be remote-controlled and diastereoselectively locked. A right-handed (P)-310 -helix is first induced in the dynamic helical oligopeptide by an l-valine (l-Val) far from the bpy moiety and the induced axial bpy chirality is diastereoselectively dioxidized. The resulting l-Val-containing linear oligopeptides at the 3,3'-positions retain their (P)-310 -helices independent of the axial chirality (aR or aS) of the N-terminal N,N'-dioxide-bpy unit, while a lactam-bridged dynamic helical oligopeptide exhibits a unique solvent-induced helix-helix transition as a result of competitive helix-inducing biases between the l-Val and (aR) or (aS)-N,N'-dioxide-bpy residues remote from each other along the entire oligopeptide chain in a tug-of-war like manner.