Stable π-Extended Thio[7]helicene-Based Diradical with Predominant Through-Space Spin-Spin Coupling.

In this work, a novel π-extended thio[7]helicene scaffold was synthesized, where the α-position of the thiophene unit could be functionalized with bulky phenoxy radicals after considerable synthetic attempts. This open-shell helical diradical, ET7H-R, possesses high stability in the air, nontrivial π conjugation, persistent chirality, and a high diradical character (y0 of 0.998). The key feature is a predominant through-space spin-spin coupling (TSC) between two radicals at the helical terminals. Variable-temperature continuous-wave electron spin resonance (cw-ESR) and superconducting quantum interference device (SQUID) magnetometry in the solid state reveal a singlet ground state with a nearly degenerate triplet state of ET7H-R. These results highlight the significance of a stable helical diradicaloid as a promising platform for investigating intramolecular TSCs.

Control of Dynamic Chirality in Donor-Acceptor Fluorophores.

Very recently, the control of dynamic chirality has emerged as a powerful strategy to design chiral functional materials. In this context, we describe herein a molecular design in which a tethered configurationally stable binaphthyl chiral unit efficiently controls the dynamic chirality of donor-acceptor fluorophores, involving diverse indolocarbazoles as electron donors and terephthalonitrile as an electron acceptor. The high conformational discrimination in such a molecular system suggested by density functional theory calculations is experimentally probed using electronic and vibrational circular dichroism and confirmed by the crystallization of these chiral molecules in gel and their single crystal X-ray diffraction analysis. In addition to extending the scope of dynamic chirality control to donor-acceptor fluorophores, this work also highlights the positive effect of the configurationally stable chiral inductor on the magnitude of the dissymmetry factors of the active dynamically chiral fluorophores, both in ground and excited states, through chiral perturbation.

Chiral perturbation on single benzene-based fluorophores: A structure/(chir)optical activity relationship study.

In this paper, we describe the synthesis and the (chir)optical properties of a novel series of circularly polarized luminescent emitters. These molecules involve a compact single benzene-based donor-acceptor fluorophore composed of two cyclic alkylamines as electron donors and a phthalonitrile moiety as electron acceptor linked to a configurationally stable BINOL acting as a chiral perturbation unit. These new compounds display fair quantum yields (up to 66%) with emission maxima around 500 nm in toluene solutions, and the study of their chiroptical properties has shown that the cyclic alkylamine's ring size affects significantly the luminescence dissymmetry factors, reaching 2.2 × 10-3 for the larger cyclic alkylamine moieties.

Synthesis, structural characterization, and chiroptical properties of planarly and axially chiral boranils.

2-Amino[2.2]paracyclophane reacts with salicylaldehyde or 2-hydroxyacetophenone to yield imines that then give access to a new series of boranils (8b-d) upon complexation with BF2 . These novel boron-containing compounds display both planar and axial chiralities and were examined experimentally and computationally. In particular, their photophysical and chiroptical properties were studied and compared to newly prepared, simpler boranils (9a-d) exhibiting axial chirality only. Less sophisticated chiral architectures were shown to demonstrate overall stronger circularly polarized luminescence (CPL) activity.

A C-H activation-based enantioselective synthesis of lower carbo[n]helicenes.

The three-dimensional structure of carbohelicenes has fascinated generations of molecular chemists and has been exploited in a wide range of applications. Their strong circularly polarized luminescence has attracted considerable attention in recent years due to promising applications in new optical materials. Although the enantioselective synthesis of fused carbo- and heterohelicenes has been achieved, a direct catalytic enantioselective method allowing the synthesis of lower, non-fused carbo[n]helicenes (n = 4-6) is still lacking. We report here that Pd-catalysed enantioselective C-H arylation in the presence of a unique bifunctional phosphine-carboxylate ligand provides a simple and general access to these lower carbo[n]helicenes. Computational mechanistic studies indicate that both the C-H activation and reductive elimination steps contribute to the overall enantioselectivity. The observed enantio-induction seems to arise from a combination of non-covalent interactions and steric repulsion between the substrate and ligand during the two key reductive elimination steps. The photophysical and chiroptical properties of the synthesized scalemic [n]helicenes have been systematically studied.

Circularly polarized-thermally activated delayed fluorescent materials based on chiral bicarbazole donors.

We describe herein a molecular design to generate circularly polarized thermally activated delayed fluorescence emitters in which chiral bicarbazole donors are connected to acceptor units via a rigid 8-membered cycle and how the nature of the donor and acceptor units affect the photophysical and chiroptical properties.