Supramolecular Control of Helicene Circularly Polarized Luminescence Emitters in Molecular Solids and Bright Nanoparticles.

Circularly polarized luminescence (CPL) from chiral molecules is attracting much attention due to its potential use in optical materials. However, formulation of CPL emitters as molecular solids typically deteriorates photophysical properties in the aggregated state leading to quenching and unpredictable changes in CPL behavior impeding materials development. To circumvent these shortcomings, a supramolecular approach can be used to isolate cationic dyes in a lattice of cyanostar-anion complexes that suppress aggregation-caused quenching and which we hypothesize can preserve the synthetically-crafted chiroptical properties.

Polycyclic Pyrazolidines by Tandem Diazomalonate Dipolar Cycloadditions and CpRu-Catalyzed Carbene Additions.

Thanks to the ability of diazo derivatives to react either as 1,3-dipoles and as carbenes after dinitrogen extrusion, combinations of oxa or aza benzonorbornadienes and diazomalonates afford polycyclic pyrazolidines via a three-step sequence of (i) a highly diastereoselective [3+2]-cycloaddition, (ii) a CpRu-catalyzed carbene addition, and (iii) a second dipolar cycloaddition. Of importance, step (II) represents a unique access to novel bench-stable N,N-cyclic azomethine imines, which behave as effective 1,3-dipoles in combination with electron-poor dipolarophiles. Each step proceeds efficiently and the 3-step process can be performed in one-pot to yield a polycyclic pyrazolidine in excellent overall yield (90 %).

Axially-chiral boramidine for detailed (chir)optical studies.

The inclusion of boron atoms into chiral π-conjugated systems is an effective strategy to unlock unique chiroptical properties. Herein, the preparation and characterization of a configurationally stable axially-chiral boramidine are reported, showcasing absorption in the UV domain, deep-blue fluorescence ( up to 94%), and |10| and values. Detailed photophysical studies and quantum-chemical calculations clearly elucidate the deactivation pathways of the emissive state to triplet excited states, involving increased spin-orbit coupling between the lowest singlet excited state and an upper triplet state.

Triple -Functionalized Cations and Neutral Radicals of Enantiopure Diaza[4]helicenes.

Modulation of absorbance and emission is key for the design of chiral chromophores. Accessing a series of compounds absorbing and emitting (circularly polarized) light over a wide spectral window and often toward near-infrared is of practical value in (chir)optical applications. Herein, by late-stage functionalization on derivatives bridging triaryl methyl and helicene domains, we have achieved the regioselective triple introduction of electron-donating or electron-withdrawing substituents.

Concave P-Stereogenic Phosphorodiamidite Ligands for Enantioselective Rh(I) Catalysis.

The development of a new class of concave P-stereogenic phosphorodiamidite ligands, derived from Tröger's bases (TBs), is explored. These ligands, characterized by their remarkable stability and unique structural geometry around the P atom, are used in asymmetric Rh(I)-catalyzed additions of boronic acids to NH-isatins resulting in excellent reactivities and reasonable enantioselectivity (er up to 92:8).