TY - JOUR
T1 - Fluorenyl-substituted silole molecules
T2 - Geometric, electronic, optical, and device properties
AU - Zhan, Xiaowei
AU - Haldi, Andreas
AU - Risko, Chad
AU - Chan, Calvin K.
AU - Zhao, Wei
AU - Timofeeva, Tatiana V.
AU - Korlyukov, Aleksander
AU - Antipin, Mikhail Yu
AU - Montgomery, Sarah
AU - Thompson, Evans
AU - An, Zesheng
AU - Domercq, Benoit
AU - Barlow, Stephen
AU - Kahn, Antoine
AU - Kippelen, Bernard
AU - Brédas, Jean Luc
AU - Marder, Seth R.
PY - 2008
Y1 - 2008
N2 - A series of silole molecules with fluorenyl substituents at varying positions - 1-(9,9-dimethylfluoren-2-yl)-1,2,3,4,5-pentaphenylsilole, 1-(fluoren-9-yl)-1,2,3,4,5-pentaphenylsilole, 1,1,3,4-tetraphenyl-2,5-bis(9,9- dimethylfluoren-2-yl)silole, and 1,1-diphenyl-2,3,4,5-tetrakis(9,9- dimethylfluoren-2-yl)silole - has been synthesized and compared to the previously reported compounds, 1,1,2,3,4,5-hexaphenylsilole and 1,1-bis(9,9-dimethylfluoren-2-yl)-2,3,4,5-tetraphenylsilole. The effect of fluorenyl substitution pattern on the geometric, thermal, electronic, optical, and electroluminescence properties was investigated both experimentally and theoretically. Analysis of the X-ray crystal packing diagrams for two new fluorenyl-substituted siloles indicates the presence of π-π stacking and CH⋯π interactions in the solid state. Across the series, excellent thermal and morphological stabilities are displayed. Photoelectron/inverse- photoelectron spectroscopy measurements and density functional theory (DFT) calculations suggest that increased conjugation length through substitution at the 2- and 5-positions plays a more significant role in tuning the ionization potentials and electron affinities of these siloles than do inductive effects through substitution of the silicon. The electronic structure (e.g., HOMO-LUMO gap) and, hence, the optical absorption and fluorescence properties are also sensitive to the positions at which the fluorenyl groups are introduced, with substitution at the 2,5-positions having the largest effect. Solution-processed electroluminescent devices fabricated with the fluorenyl-substituted siloles as the emissive layer have luminous efficiencies as high as 3.6 cd A-1.
AB - A series of silole molecules with fluorenyl substituents at varying positions - 1-(9,9-dimethylfluoren-2-yl)-1,2,3,4,5-pentaphenylsilole, 1-(fluoren-9-yl)-1,2,3,4,5-pentaphenylsilole, 1,1,3,4-tetraphenyl-2,5-bis(9,9- dimethylfluoren-2-yl)silole, and 1,1-diphenyl-2,3,4,5-tetrakis(9,9- dimethylfluoren-2-yl)silole - has been synthesized and compared to the previously reported compounds, 1,1,2,3,4,5-hexaphenylsilole and 1,1-bis(9,9-dimethylfluoren-2-yl)-2,3,4,5-tetraphenylsilole. The effect of fluorenyl substitution pattern on the geometric, thermal, electronic, optical, and electroluminescence properties was investigated both experimentally and theoretically. Analysis of the X-ray crystal packing diagrams for two new fluorenyl-substituted siloles indicates the presence of π-π stacking and CH⋯π interactions in the solid state. Across the series, excellent thermal and morphological stabilities are displayed. Photoelectron/inverse- photoelectron spectroscopy measurements and density functional theory (DFT) calculations suggest that increased conjugation length through substitution at the 2- and 5-positions plays a more significant role in tuning the ionization potentials and electron affinities of these siloles than do inductive effects through substitution of the silicon. The electronic structure (e.g., HOMO-LUMO gap) and, hence, the optical absorption and fluorescence properties are also sensitive to the positions at which the fluorenyl groups are introduced, with substitution at the 2,5-positions having the largest effect. Solution-processed electroluminescent devices fabricated with the fluorenyl-substituted siloles as the emissive layer have luminous efficiencies as high as 3.6 cd A-1.
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U2 - 10.1039/b803470b
DO - 10.1039/b803470b
M3 - Article
AN - SCOPUS:45749147389
SN - 0959-9428
VL - 18
SP - 3157
EP - 3166
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
IS - 26
ER -