Kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cages.

The kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cage compounds, measured in terms of ΔΔG‡on, is determined by the planar-chirality of the host and influenced by the size, as measured by ion mobility-mass spectrometry, but not the chirality of its substituents.

Enantioselective synthesis of chiral porphyrin macrocyclic hosts and kinetic enantiorecognition of viologen guests.

The construction of macromolecular hosts that are able to thread chiral guests in a stereoselective fashion is a big challenge. We herein describe the asymmetric synthesis of two enantiomeric C 2-symmetric porphyrin macrocyclic hosts that thread and bind different viologen guests. Time-resolved fluorescence studies show that these hosts display a factor 3 kinetic preference (ΔΔG ‡ on = 3 kJ mol-1) for threading onto the different enantiomers of a viologen guest appended with bulky chiral 1-phenylethoxy termini. A smaller kinetic selectivity (ΔΔG ‡ on = 1 kJ mol-1) is observed for viologens equipped with small chiral sec-butoxy termini. Kinetic selectivity is absent when the C 2-symmetric hosts are threaded onto chiral viologens appended with chiral tails in which the chiral moieties are located in the centers of the chains, rather than at the chain termini. The reason is that the termini of the latter guests, which engage in the initial stages of the threading process (entron effect), cannot discriminate because they are achiral, in contrast to the chiral termini of the former guests. Finally, our experiments show that the threading and de-threading rates are balanced in such a way that the observed binding constants are highly similar for all the investigated host-guest complexes, i.e. there is no thermodynamic selectivity.

Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach.

Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations. This host-guest binding also leads to unusual enhanced vibrational circular dichroism, which is the result of a combination of phenomena, such as rigidification of the host and guest structures, charge transfer, and coupling of specific vibration modes of the host and guest. The results offer insights in how the porphyrin cage-compounds may be used to construct a future molecular Turing machine that can write chiral information onto polymer chains.

Reversible Stereodivergent Cycloaddition of Racemic Helicenes to [60]Fullerene: A Chiral Resolution Strategy.

[60]Fullerene and its rarely explored reversible covalent chemistry have been harnessed as an efficient alternative for the chiral resolution of racemates. By using only catalytic amounts of chiral agents, stereodivergent 1,3-dipolar cycloadditions of racemic helicenes onto [60]fullerene were carried out. The formed helicene/fullerene diastereomers were easily separated by conventional chromatography, and afterward, a simple catalyzed 1,3-dipolar retro-cycloaddition afforded helicene starting materials in high optical purity.

Synthesis of a Helical Bilayer Nanographene.

A rigid, inherently chiral bilayer nanographene has been synthesized as both the racemate and enantioenriched M isomer (with 93 % ee) in three steps from established helicenes. This folded nanographene is composed of two hexa-peri-hexabenzocoronene layers fused to a [10]helicene, with an interlayer distance of 3.6 Šas determined by X-ray crystallography. The rigidity of the helicene linker forces the layers to adopt a nearly aligned AA-stacked conformation, rarely observed in few-layer graphene. By combining the advantages of nanographenes and helicenes, we have constructed a bilayer system of 30 fused benzene rings that is also chiral, rigid, and remains soluble in common organic solvents. We present this as a molecular model system of bilayer graphene, with properties of interest in a variety of potential applications.