Confined Lewis Pairs: Investigation of the X →Si Interaction in Halogen-Encapsulating Silafulleranes.

A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si Y ] (X=F-I; Y=F-I, H, Me, Et) and -[Cl@Si H Y ] (Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl in a systematic series of concave silapolyquinane model systems. Second, we investigated the X →Si interaction energy ( ) as a function of X and Y and found the largest values for electron-withdrawing exohedral substituents Y.

Brominated [20]silafulleranes: pushing the limits of steric loading.

Starting from the perhydrogenated silafullerane [BuN][Cl@Si(SiH)H], treatment with BBr leads to partially and exhaustively brominated clusters, [BuN][Cl@Si(SiBrH)Br] (120 eq. BBr, room temperature, 30 min) and [BuN][Cl@Si(SiBr)Br] (300 eq. BBr, 130 °C, 3 d).

Regioselective Derivatization of Silylated [20]Silafulleranes.

Silafulleranes with endohedral Cl ions are a unique, scarcely explored class of structurally well-defined silicon clusters and host-guest complexes. Herein, we report regioselective derivatization reactions on the siladodecahedrane [BuN][Cl@Si(SiCl)Cl] ([BuN][]), which has its cluster surface decorated with 12 SiCl and 8 Cl substituents in perfect symmetry. The room-temperature reaction of [BuN][] with excess BuAlH in -difluorobenzene (DFB) furnishes perhydrogenated [BuN][Cl@Si(SiH)H] ([BuN][]) in 50% yield; the non-pyrophoric [] is the largest structurally authenticated (by X-ray diffraction) hydridosilane known to date.

[Cl@SiH]: Parent Siladodecahedrane with Endohedral Chloride Ion.

Fullerenes and diamondoids are at the core of nanoscience. Comparable monodisperse silicon analogues are scarce. Herein, we report the synthesis of the parent siladodecahedrane, which represents the largest Platonic solid.

Selective access to either a doubly boron-doped tetrabenzopentacene or an oxadiborepin from the same precursor.

The well-known red emitter tetrabenzo[,,,]pentacene () has been transformed into a bright blue emitter (; λ = 472 nm; c-hexane) substitutional doping with two boron atoms. In contrast to the electron-rich , which forms -peroxides with O under daylight, the benchtop-stable is a good electron acceptor and undergoes reversible reduction at a moderate half-wave potential of = -1.73 V ( FcH/FcH; THF).