Polycationic Open-Shell Cyclophanes: Synthesis of Electron-Rich Chiral Macrocycles, and Redox-Dependent Electronic States.

π-Conjugated chiral nanorings with intriguing electronic structures and chiroptical properties have attracted considerable interests in synthetic chemistry and materials science. We present the design principles to access new chiral macrocycles (1 and 2) that are essentially built on the key components of main-group electron-donating carbazolyl moieties or the π-expanded aza[7]helicenes. Both macrocycles show the unique molecular conformations with a (quasi) figure-of-eight topology as a result of the conjugation patterns of 2,2',7,7'-spirobifluorenyl in 1 and triarylamine-coupled aza[7]helicene-based building blocks in 2.

Chiral Luminescent Aza[7]helicenes Functionalized with a Triarylborane Acceptor and Near-Infrared-Emissive Doublet-State Radicals.

This paper presents new chiral luminescent molecules ( and ) using configurationally stable aza[7]helicene () as a universal heteroatom-doped chiral scaffold. The respective reactions of electron-donating with a triarylborane acceptor via palladium-catalyzed Buchwald-Hartwig C-N coupling and with the open-shell doublet-state TTM radical via nucleophilic aromatic substitution (S2Ar) resulted not only in tunable emissions from blue to the NIR domain but also in significantly enhanced emission quantum efficiency up to Φ = 50%.

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations.

Highly emissive π-conjugated macrocycles with tunable circularly polarized luminescence (CPL) have sparked theoretical and synthetic interests in recent years. Herein, we report a synthetic approach to obtain new chiral organoborane macrocycles (, , and ) that are built on the structurally chiral [5]helicenes and highly luminescent triarylborane/amine moieties embedded into the cyclic systems. These rarely accessible B/N-doped main-group chiral macrocycles show a unique topology dependence of the optoelectronic and chiroptical properties.