Effect of the Tris(trimethylsilyl)silyl Group on the Fluorescence and Triplet Yields of Oligothiophenes

The origin of the large difference of room-temperature fluorescence yields (Φf(RT)) among tris(trimethylsilyl)silylated oligothiophene derivatives was investigated. Tris(trimethylsilyl)silylated thiophene (1) and tris(trimethylsilyl)silylated terthiophene (3) show low fluorescence yields while that of tris(trimethylsilyl)silylated bithiophene (2) is high. Nanosecond transient absorption measurements for 2 and 3 verified that the large difference between their intersystem crossing (ISC) rates from the lowest singlet excited state (S1) causes the large difference in Φf(RT). Quantum calculations indicated that the Si–Si σ bond of (Me3Si)3Si, corresponding to the highest occupied molecular orbital (HOMO), is closely involved in the ISC from S1. The planar conjugated core having much higher or comparable HOMO energy relative to the (Me3Si)3Si substituent, such as 1 and 3, induces large spin–orbit coupling (SOC) between S1 and the second-order triplet excited state (T2), resulting in fast ISC from S1 leading to...