(Oligo)aromatic species with one or two conjugated SiSi bonds: near-IR emission of anthracenyl-bridged tetrasiladiene12. Issue 27 (7th April 2017)

• Record Type: Journal Article
• Authors: Obeid, Naim M.; Klemmer, Lukas; Maus, Daniel; Zimmer, Michael; Jeck, Jonathan; Bejan, Iulia; White, Andrew J. P.; Huch, Volker; Jung, Gregor; Scheschkewitz, David
• Is Part Of: Dalton transactions. Volume 46:Issue 27(2017)
• Page Start: 8839
• Page End: 8848
• Publication Date: 2017-04-07
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00397h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : SiSi transfer to bulky (poly)aromatic substrates is described. Some products show intermolecular charge transfer bands and weak fluorescence. Abstract : A series of aryl disilenes Tip2 SiSi(Tip)Ar (2a–c ) and para -arylene bridged tetrasiladienes, Tip2 SiSi(Tip)–LU–Si(Tip)SiTip2 (3a–d ) are synthesized by the transfer of the Tip2 SiSiTip unit to aryl halides and dihalides by nucleophilic disilenides Tip2 SiSiTipLi (Tip = 2, 4, 6-iPr3 C6 H2, Ar = aryl substituent, LU = para -arylene linking unit). The scope of the nucleophilic SiSi transfer reaction is demonstrated to also include substrates of considerable steric bulk such as mesityl or duryl halides Ar–X (Ar = Mes = 2, 4, 6-Me3 C6 H2 ; Ar = Dur = 2, 3, 5, 6-Me4 C6 H, X = Br or I). Bridged tetrasiladienes Tip2 SiSi(Tip)–LU–Si(Tip)SiTip2 with more extended linking units surprisingly exhibit fluorescence at room temperature, albeit weak. DFT calculations suggest that partial charge transfer character of the excited state is a possible explanation.