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(Z)-1,2-Di(1-pyrenyl)disilene: Synthesis, Structure, and Intramolecular Charge-Transfer Emission
Megumi Kobayashi1, Naoki Hayakawa2, Tsukasa Matsuo1,2,3
1Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute , 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Abstract:
(Z)-1,2-Di(1-pyrenyl)disilene containing bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl (Eind) groups has been obtained as purple crystals by the reductive coupling reaction of the corresponding dibromosilane with lithium naphthalenide. An X-ray crystallographic analysis revealed an Eind- and pyrenyl-meshed molecular gear around the disilene core adopting the Z configuration, in which the two pyrenyl groups intramolecularly interact through the π-π stacking with a distance of 3.635 Å between the centers of the two pyrene rings. The disilene π-system exhibits a π(Si-Si) → π*(pyrene) intramolecular charge-transfer (ICT) fluorescence at room temperature, whose wavelengths depend on the solvent polarity. The photophysical properties are theoretically supported by computational studies including excited-state calculations.
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