Non-Planar [n]Cyclo-1,8-carbazolylenes (n=3,4,6) and [3]Cyclo-1,8-carbazolylenyl B, P, PO, SiPh Complexes

A new family of non-planar heterocyclic molecules consisting of carbazoles was created. A bowl-shaped cyclodimer, a flake-shaped cyclotrimer, a double-decker-ring-shaped cyclotetramer and a cyclohexamer were synthesized by Ni⁰-mediated one-shot cyclo-oligomerization of 1,8-dibromocarbazole, and were named [n]cyclo-1,8-carbazolylenes (n=3,4,6). [3]Cyclo-1,8-carbazolylene was found to act as a trivalent tridentate ligand for heteroatoms (B, P, Si), giving flake-shaped complexes. The boron derivative acted as a Lewis acid, and the tetra-coordinated complexes showed an unprecedented red-shift of absorption and emission spectra by the coordination. The synthetic method, the distorted C₂ or C₁ symmetric shape, the trivalent tridentate coordination ability and the kinds of introduced heteroatoms of [3]cyclo-1,8-carbazolylenes, the electronic structure, the photophysical property, and the Lewis acidity were distinct from those of related subporphyrins/subphthalocyanines.