Flexible and rigid "chirally distorted" π-systems: binaphthyl conjugates as organic CPL-active chromophores.

The inclusion of high-performance dyes into chiral π-conjugated systems is an effective strategy for activating significant chiroptical properties. We report the preparation and characterization of configurationally stable, axially-chiral π-conjugated systems in which acridone or 2,5-diarylamino-terephthalate has been fused into the chiral scaffold of a 1,1'-binaphthyl moiety. The high-yielding synthesis afforded π-conjugated systems with characteristics essentially matching those of the parent dyes while introducing detectable CPL activity in solution.

One-Handed Covalent Helical Ladder Polymers: The Dawn of a Tailorable Class of Chiral Functional Materials.

In the last decades, chemists have developed methods to synthesize helical molecular architectures using a combination of covalent and non-covalent interactions. Very recently, the new class of completely covalent, one-handed helical ladder polymers has vigorously emerged. Such polymers can be rationally and programmably obtained through an approach guided by the principles of chirality-assisted-synthesis (CAS) and making use synergically of two disciplines that have so far rarely interacted: non-planar chiral π-conjugated synthons and ladder polymer chemistry.

Triptycene-based diiron(II) mesocates: spin-crossover in solution.

Triptycene-based diiron(II) and dizinc(II) mesocates were obtained using a novel rigid ligand with two pyridylbenzimidazole chelating units fused into the triptycene scaffold. Studies on the diiron(II) assembly in solution showed that the complex undergoes thermal-induced one-step spin-crossover with at 243 K (Evans method).

Homoconjugation and Tautomeric Isomerism in Triptycene-Fused Pyridylbenzimidazoles.

The facile, metal-free synthesis and characterization of three new series of triptycene-fused pyridylbenzimidazoles are reported; such compounds possess an imidazole moiety fused within the benzene rings of the trypticene and a pyridine ring installed at position 2 of the imidazole rings. The position of the nitrogen atom of the pyridyl moiety linked to position 2 of the fused benzimidazole scaffold is systematically changed from the to position. The number of substituted blades bearing the pyridyl-substituted fused benzimidazole scaffolds has been increased from one to three.

Enabling Stereochemical Communication and Stimuli-Responsive Chiroptical Properties in Biphenyl-Capped Cyclodextrins.

Chiroptical materials are gaining increasing interest due to their innovative character and their applications in optoelectronics and data encryption technologies. Fully harnessing the potential of building blocks from the "chiral pool", such as native cyclodextrins (CDs), as they often lack chromophores suitable for the construction of materials with significant chiroptical properties. Here, we present the synthesis and characterization of a two-level molecular stack consisting of a point-chiral element (CD) and an axially chiral element (biphenyl), capable of effectively translating the overall stereochemical information contained in CDs into stimuli-responsive chiroptical properties.

Activation of Solid-State Emission and Photostability through Molecular Confinement: The Case of Triptycene-Fused Quinacridone Dyes.

We report the facile, metal-free convergent synthesis and the characterization of novel quinacridone dyes in which two triptycene units end-cap and sterically confine the quinacridone chromophore. A precise comparison of the confined dyes with their known homologues reveals that the reduction of π-π interactions in triptycene-fused quinacridone dyes compared to classical quinacridone results not only in an increase of solubility and processability but also in an enhancement of fluorescence quantum yield and photostability in the solid state.

Chiroptical sensing of perrhenate in aqueous media by a chiral organic cage.

A chiral cage is proposed as an effective chiroptical sensor for perrhenate (surrogate for TcO) in water, fruit juice and artificial urine media. The key mechanism for the chiroptical sensing resides in the change of dihedral angle of the binaphthyl unit and H-bonds with the guest, resulting in ample changes of the CD signal as a consequence of the binding event.

Triptycene derivatives as chiral probes for studying the molecular enantiorecognition on sub-2-μm particle cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase.

Two chiral triptycene derivatives were analyzed on the Chiralpak IB-U column packed with cellulose tris(3,5-dimethylphenylcarbamate)-based sub-2-μm diameter particles. Under normal-phase conditions, sub-minute baseline enantioseparations were obtained. Differences in structural elements and chromatographic behavior of the investigated compounds were evaluated to identify the interactions that drive the chiral discrimination process.

Chiral Triptycenes in Supramolecular and Materials Chemistry.

Triptycenes are an intriguing class of organic molecules with several unusual characteristics, such as a propeller-like shape, saddle-like cavities around a symmetrical scaffold, a rigid π-framework. They have been extensively studied and proposed as key synthons for a variety of applications in supramolecular chemistry and materials science. When decorated with an appropriate substitution pattern, triptycenes can be chiral, and, similarly to other popular chiral π-extended synthons, can express chirality robustly, efficiently, and with relevance to chiroptical spectroscopies.