TY - JOUR

T1 - Synthesis and photophysical properties of copolyfluorenes for light-emitting applications: Spectroscopic experimental study and theoretical DFT consideration

AU - Smyslov, Ruslan Yu.

AU - Tomilin, Felix N.

AU - Shchugoreva, Irina A.

AU - Nosova, Galina I.

AU - Zhukova, Elena V.

AU - Litvinova, Larisa S.

AU - Yakimansky, Alexander V.

AU - Kolesnikov, Ilya

AU - Abramov, Igor G.

AU - Ovchinnikov, Sergei G.

AU - Avramov, Paul V.

PY - 2019

Y1 - 2019

N2 - Using Suzuki and Yamamoto coupling reactions, copoly-(9,9-dioctylfluorenes) (CPF) were synthesized and compared regarding their photophysical properties using the spectroscopic and ab initio DFT approaches. The CPFs were functionalized by benzo [2,3,5] thiadiazole (BT) or carbazole-3,6-diyl (3,6-Cz). The latter was used to introduce different luminophore fragments, including Nile red and 4-pyrrolidinyl-1,8-naphthalimide derivatives. The effect of the two synthesis techniques on the polymer microstructure, the influence of embedding of 3,6-Cz moieties in the polymer backbone on polymer structuring, and the impact of the end groups like novel quinoxaline-containing compounds on the luminescent properties of CPFs were investigated. By comparing electron density distribution using the ab initio DFT approach with photoluminescence, it was shown that Suzuki reaction provides a chain microstructure with individual BT fragments separated by 9,9-dioctylfluorene monomeric units, while Yamamoto reaction leads to the blocks of BT units. This effect leads to different CPF photophysical properties (absorption and emission spectra).

AB - Using Suzuki and Yamamoto coupling reactions, copoly-(9,9-dioctylfluorenes) (CPF) were synthesized and compared regarding their photophysical properties using the spectroscopic and ab initio DFT approaches. The CPFs were functionalized by benzo [2,3,5] thiadiazole (BT) or carbazole-3,6-diyl (3,6-Cz). The latter was used to introduce different luminophore fragments, including Nile red and 4-pyrrolidinyl-1,8-naphthalimide derivatives. The effect of the two synthesis techniques on the polymer microstructure, the influence of embedding of 3,6-Cz moieties in the polymer backbone on polymer structuring, and the impact of the end groups like novel quinoxaline-containing compounds on the luminescent properties of CPFs were investigated. By comparing electron density distribution using the ab initio DFT approach with photoluminescence, it was shown that Suzuki reaction provides a chain microstructure with individual BT fragments separated by 9,9-dioctylfluorene monomeric units, while Yamamoto reaction leads to the blocks of BT units. This effect leads to different CPF photophysical properties (absorption and emission spectra).

KW - Density functional theory

KW - Suzuki cross-coupling

KW - Yamamoto polycondensation

UR - http://www.scopus.com/inward/record.url?scp=85061964429&partnerID=8YFLogxK

U2 - 10.1016/j.polymer.2019.02.015

DO - 10.1016/j.polymer.2019.02.015

M3 - Article

VL - 168

SP - 185

EP - 198

JO - Polymer

JF - Polymer

SN - 0032-3861

ER -