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Published on: August 19, 2013
Tetrel Bond-Mediated Photophysical Modulation and Fluoride Recognition in Carbazole-Organosilanes
Md Hasanul Haque1, Thien D Nguyen1, Benjamin T Diroll2
1Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, Texas 76019, United States.
None:
Silicon-centered orbitals are typically regarded as electronically inert in donor-acceptor systems. Here, we show that silole-based carbazole-silane architectures can render these orbitals electronically relevant, enabling modulation of excited-state behavior and anion-responsive photophysics. Two carbazole-Dipp-silanes exhibit identical carbazole-localized LE singlet emission in solution yet diverge markedly in the solid state: one compound displays a broad long-wavelength emission band in the prompt spectrum and enhanced long-lived emission consistent with a triplet-derived excited state, likely arising from a combination of intramolecular structural locking and solid-state packing effects, whereas the more flexible analogue remains predominantly LE-emissive. Fluoride coordination further differentiates the two systems, producing ratiometric red-shifted emission in one case and fluorescence quenching in the other through a fully reversible coordination process. These results identify σ*(Si-Ar) orbitals as tunable contributors to excited-state landscapes in organosilane luminophores and suggest a broader design strategy for controlling excited-state behavior in tetrel-based photofunctional systems.
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