The sila-functional 9,10-disilylanthracenes An(SiR 2 X) 2 (1, R ) i-Pr, X ) H; 2, R ) i-Pr, X ) Cl; 3, R ) Me, X ) H) were synthesized, and the X-ray structure is reported for 1. Compounds 1-3 as well as the related compound An(SiMe 3 ) 2 exhibit intense fluorescence (Φ f > 0.9) at room temperature.

A carbon-carbon double bond consists of a σ bond and a π bond. Recently, the concept of a π single bond, where a π bond is not accompanied by a σ bond, has been proposed in diradicals containing carbon and heteroatom radical centers. Here we report a closed-shell compound having a silicon-silicon π single bond. 1,2,2,3,4,4-Hexa-tert-butylbicyclo[1.1.0]tetrasilane has a silicon−silicon π single bond between the bridgehead silicon atoms. The X-ray crystallographic analysis shows that the silicon−silicon π single bond (2.853(1) Å) is far longer than the longest silicon−silicon bond so far reported. In spite of this unusually long bond length, the electrons of the 3p orbitals are paired, which is confirmed by measurement of electron paramagnetic resonance, and magnetic susceptibility and natural bond orbital analysis. The properties of the silicon−silicon π single bond are studied by UV/Vis and 29 Si NMR spectroscopy, and theoretical calculations.

Cyclopentasilane-fused hexasilabenzvalene 1 was synthesized by the reduction of tetrachlorocyclopentasilane 6 in 19% yield as a green powder. The molecular structure and properties of 1 were studied by spectroscopic and X-ray crystallographic analyses. Theoretical calculations of the model and real molecules of 1 and their structural isomers 12–16 suggest that the linkage of the central hexasilabenzvalene moiety with trisilane chains and the introduction of tert-butyl groups affect their relative energies.