A series of (E)-1,2-diaryldigermenes incorporating bulky Eind groups: structural characteristics and absorption properties

Abstract

A series of (E)-1,2-diaryldigermenes, (Eind)ArGeGeAr(Eind) [Ar = phenyl (2), thiophen-2-yl (3), 9,9-dimethyl-2-fluorenyl (4) and 2,2′-bithiophen-5-yl (5)], supported by the fused-ring bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl (Eind) groups, have been obtained as yellow-orange to red crystalline solids by the reaction of 1,2-dibromodigermene, (Eind)BrGeGeBr(Eind) (1), with ArLi. In the crystals of 2–5, the digermene cores show a flexible nature adopting a trans-bent geometry with the trans-bent angles (θ) between the Ge–Ge vector and the C_Eind–Ge–C_Ar plane of 34.04(12)° (2), 38.3(3)° and 38.8(3)° (3), 33.69(12)° (4) and 39.30(13)° (5). In the UV-vis spectra, strong π–π* absorptions have been observed with an absorption maximum at 451 nm (ε = 1.3 × 10⁴) (2), 455 nm (ε = 9.7 × 10³) (3), 480 nm (ε = 1.3 × 10⁴) (4) and 497 nm (ε = 1.4 × 10⁴) (5), retaining the GeGe double bond in solution. The absorption data and DFT calculations provide evidence for the intrinsic π-conjugation between the GeGe chromophore and aromatic rings involving the narrowing of the HOMO–LUMO gaps (ΔE) with the extension of the carbon π-electron systems.