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- W2999127959 abstract "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 a small Φf(RT). However, a planar conjugated core having slightly higher HOMO energy than that of the (Me3Si)3Si substituent, such as 2, minimizes SOC between S1 and T2, resulting in slow ISC from S1 leading to a large Φf(RT). Thus, the relationship between the HOMO level of the (Me3Si)3Si substituent and that of the planar conjugated core is key to controlling the ISC from S1." @default.
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- W2999127959 date "2020-01-09" @default.
- W2999127959 modified "2023-10-18" @default.
- W2999127959 title "Effect of the Tris(trimethylsilyl)silyl Group on the Fluorescence and Triplet Yields of Oligothiophenes" @default.
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- W2999127959 doi "https://doi.org/10.1021/acs.jpcc.9b10718" @default.
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