Fast Singlet Exciton Decay in Push鈥揚ull Molecules Containing Oxidized Thiophenes

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• 作者：Erik Busby ; Jianlong Xia ; Jonathan Z. Low ; Qin Wu ; Jessica Hoy ; Luis M. Campos ; Matthew Y. Sfeir
• 刊名：Journal of Physical Chemistry B
• 出版年：2015
• 出版时间：June 18, 2015
• 年：2015
• 卷：119
• 期：24
• 页码：7644-7650
• 全文大小：378K
• ISSN：1520-5207

文摘

A common synthetic strategy used to design low-bandgap organic semiconductors employs the use of 鈥減ush鈥損ull鈥?building blocks, where electron -rich and electron-deficient monomers are alternated along the 蟺-conjugated backbone of a molecule or polymer. Incorporating strong 鈥減ull鈥?units with high electron affinity is a means to further decrease the optical gap for infrared optoelectronics or to develop n-type semiconducting materials. Here we show that the use of thiophene-1,1-dioxide as a strong acceptor in 鈥減ush鈥損ull鈥?oligomers affects the electronic structure and carrier dynamics in unexpected ways. Critically, the overall excited-state lifetime is reduced by several orders of magnitude relative to unoxidized analogs due to the introduction of low-energy optically dark states and low-energy triplet states that allow for fast internal conversion and intramolecular singlet fission. We found that the electronic structure and excited-state lifetime are strongly dependent on the number of sequential thiophene-1,1-dioxide units. These results suggest that both the static and dynamical optical properties are highly tunable via small changes in chemical structure that have drastic effects on the optoelectronic properties, which can impact the types of applications that involve these materials.