Structures and Optical Properties
of Tris(trimethylsilyl)silylated
Oligothiophene Derivatives
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Abstract
The structures and optical properties
of tris(trimethylsilyl)silylated
oligothiophenes were examined by spectroscopies, theoretical calculations,
and single-crystal X-ray measurements. Bathochromic shift from the
original oligothiophenes was observed in the tris(trimethylsilyl)silylated
ones, confirming the σ–π conjugation between Si–Si
σ bonds and π-orbital. 5,5′-Bis(tris(trimethylsilyl)silyl)-2,2′-bithiophene
(<b>Si-T</b><sub><b>2</b></sub>) showed the highest fluorescence
quantum yield (Φ<sub>F</sub>) both in solution (0.67, excited
at 350 nm) and the solid state (0.74, excited at 371 nm). The introduction
of tris(trimethylsilyl)silyl groups led to the small nonradiative
rate constant of <b>Si-T</b><sub><b>2</b></sub>, resulting
in the high Φ<sub>F</sub> in the solution state. <b>Si-T</b><sub><b>2</b></sub> also exhibited effective σ–π
conjugation and poor molecular interaction, which reflected its high
Φ<sub>F</sub> in the solid state. On the contrary, lower Φ<sub>F</sub> (0.13, excited at 331 nm) in the solid state was observed
in the longest oligothiophene examined, 5,5‴-bis(1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilan-2-yl)-2,2′:5′,2″:5″,2‴-quaterthiophene
(<b>Si-T</b><sub><b>4</b></sub>). Single-crystal X-ray
measurement clarified that this compound adopted a zigzag packing
structure and a rare <i>syn-anti-syn</i> conformation, which
led to the poor σ–π conjugation and the decrease
of π-orbital overlap in the solid state