Synthesis, characterization and solid-state emission properties of arylsilyl-substituted pyrene derivatives

• Synthesis, properties and theoretical analyses of arylsilyl pyrenes are described.
• Triphenylsilylphenyl pyrene exhibits efficient solid-state emission with Φ of 0.65.
• The fluorescence properties of silylalkynyl pyrene are solvent polarity dependent.
• Michl's perimeter model was used to describe the electronic structures of pyrene.
• MCD, CV and TD-DFT have been used to analyze the structure–property relationships.

Arylsilyl substituted pyrene derivatives were synthesized via Suzuki-Miyaura and Hagihara-Sonogashira cross-coupling reactions with boronic acid-terminated and ethynyl-terminated tetraphenylsilane at the 1-, 3-, 6- and 8-positions. The spectroscopic properties of the dyes were investigated in various solvents and in films to assess the suitability of these compounds for optoelectronic applications. A triphenylsilylphenyl substituted pyrene was found to exhibit intense emission in the solid state with an absolute fluorescence quantum yield (ΦF) of 0.65. In contrast, the emission properties of a triphenylsilylphenyl(ethynyl) substituted pyrene were found to be somewhat weaker in the solid state (ΦF = 0.16) and solvent polarity dependent in solution. Magnetic circular dichroism (MCD) spectroscopy, cyclic voltammetry, and theoretical calculations have been used to analyze the structure-property relationships with Michl's perimeter model used as a conceptual framework for rationalizing the key trends.

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