Carbo-mer of Barrelene: A Rigid 3D-Carbon-Expanded Molecular Barrel.

After extensive studies of 1D and 2D skeletal carbo-mers based on C8 π-conjugating dialkynylbutatriene units (DABs: ∼C≡C-(R)C=C=C=C(R)-C≡C∼) bridging sp or sp2 centers in carbo-butene, carbo-xylylene or carbo-benzene derivatives, 3D versions are envisaged through carbo-barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp3 carbinol vertices or ether thereof. For R=Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Šhigh C26 barrel-shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host-guest supramolecular chemistry and single molecule charge transport.

Distannabarrelenes with Three Coordinated SnII Atoms.

Crystalline 1,4-distannabarrelene compounds [(ADCAr )3 Sn2 ]SnCl3 (3-Ar) (ADCAr ={ArC(NDipp)2 CC}; Dipp=2,6-iPr2 C6 H3 , Ar=Ph or DMP; DMP=4-Me2 NC6 H4 ) derived from anionic dicarbenes Li(ADCAr ) (2-Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3-Ar features a barrelene framework with three coordinated SnII atoms at the 1,4-positions, whereas the anionic unit SnCl3 is formally derived from SnCl2 and chloride ion. The all carbon substituted bis-stannylenes 3-Ar have been characterized by NMR spectroscopy and X-ray diffraction. DFT calculations reveal that the HOMO of 3-Ph (ϵ=-6.40 eV) is mainly the lone-pair orbital at the SnII atoms of the barrelene unit. 3-Ar readily react with sulfur and selenium to afford the mixed-valence SnII /SnIV compounds [(ADCAr )3 SnSn(E)](SnCl6 )0.5 (E=S 4-Ar, Ar=Ph or DMP; E=Se 5-Ph).