1. A series of (E)-1,2-diaryldigermenes incorporating bulky Eind groups: structural characteristics and absorption properties.
- Author
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Yagura, Shogo, Hayakawa, Naoki, Kuroda, Airi, Ota, Kei, Tanishita, Rhota, Urasaki, Genya, Nakahodo, Tsukasa, Nakai, Hidetaka, Hoshino, Manabu, Hashizume, Daisuke, and Matsuo, Tsukasa
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- *
CRYSTALS , *ABSORPTION , *DOUBLE bonds - Abstract
A series of (E)-1,2-diaryldigermenes, (Eind)ArGe=GeAr(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)BrGe=GeBr(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 () between the Ge–Ge vector and the CEind–Ge–CAr 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 Ge=Ge double bond in solution. The absorption data and DFT calculations provide evidence for the intrinsic π-conjugation between the Ge=Ge chromophore and aromatic rings involving the narrowing of the HOMO–LUMO gaps (ΔE) with the extension of the carbon π-electron systems. [ABSTRACT FROM AUTHOR]
- Published
- 2022
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