Stereoselective Nanocarbon Imides Featuring 12-fold [5]helicenes

Despite the great progress in research on chiral molecular nanocarbons containing multiple helicenes, controlling the stereoselectivity is still a major challenge, especially when attempting to increase the number of helicene moieties. Herein, a novel molecular nanocarbon imides composed of C204 skeleton and eighteen imide groups was successfully synthesized via an inside–out ring closing strategy involving repeated Suzuki–Miyaura coupling for C–C bond formation and photocyclic aromatization. Because of the presence of quad–core twelvefold [5]helicenes, there are, in theory, more than one hundred stereoisomers. However, only one pair of stereoisomers with D3 symmetry was observed. Despite the large and rigid skeleton, the (3M,3M,3M,3M)+(3P,3P,3P,3P) enantiomers were successfully separated by chiral HPLC, and the chiroptical properties were investigated by CD spectroscopy.

Engineering chiral plasmonic nanostructures for gain-assisted plasmon amplification and tunable enhancement of circular dichroism

Circular dichroism (CD) from plasmonic nanostructures yields fascinating insights into their chiroptical properties, however, the weak signals make their investigations profoundly challenging. We have demonstrated a method for significantly improving...

Interparticle Gap Geometry Effects on Chiroptical Properties of Plasmonic Nanoparticle Assemblies

Chiral linear assemblies of plasmonic nanoparticles with chiral optical activity often show low asymmetry factors. Systematic understanding of the structure-property relationship in these systems must be improved to facilitate rational design of their chiroptical response. Here we study the effect of large-area interparticle gaps in chiral linear nanoparticle assemblies on their chiroptical properties using a tetrahelix structure formed by a linear face-to-face assembly of nanoscale Au tetrahedra. Using finite-difference time-domain and finite element methods, we performed in-depth evaluation of the extinction spectra and electric field distribution in the tetrahelix structure and its dependence on various geometric parameters. The reported structure supports various plasmonic modes, one of which shows a strong incident light handedness selectivity that is associated with large face-to-face junctions. This works highlights the importance of gap engineering in chiral plasmonic assemblies to achieve g-factors greater than 1 and produce structures with a handedness-selective optical response.

One-Pot Preparation of (NH)-Phenanthridinones and Amide-Functionalized [7]Helicene-like Molecules from Biaryl Dicar-boxylic Acids

A one-pot transformation of biaryl dicarboxylic acids to (NH)-phenanthridinone derivatives based on a Curtius rearrangement and subsequent basic hydrolysis was developed. This method is also applicable for the preparation of optically active amide-functionalized [7]helicene-like molecules. Furthermore, aza[5]helicene derivatives with a phosphate moiety were isolated as a product of the Curtius rearrangement step in the case of substrates that bear chalcogen atoms. The stereostructures of these products, revealed by X-ray diffraction analysis, suggested that chalcogen-bonding and pnictogen-bonding interactions might contribute to their stabilization. The configurational stability of the helicene-like molecules and their chiroptical properties were further investigated.