Browsing by Author "Hsu, Tze-Gang"

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Regio- and stereo-selective [4+4] photodimerization of angular-shaped dialkyltetracenedithiophene
(2019-01-11)
Hsu, Tze-Gang
;
Chou, Hsiao-Chieh
;
Liang, Ming-Ju
;
Lai, Yu-Ying
;
Cheng, Yen-Ju
Angular-shaped dialkyltetracenedithiophenes (aTDTs) undergo [4+4] photodimerization in solution to form a butterfly-shaped skeleton. This reaction proceeds in a regio- and stereo-selective manner, forming only a single planosymmetric syn-[2,2]-daTDT out of six possible products. The photocycloaddition of aTDTs can take place topochemically in the thin-film state while maintaining regio- and stereo-selectivity. Stronger aliphatic dispersion forces and - interactions play important roles in forming the eclipsed dimeric complex that leads to the syn-[2,2]-daTDT isomer.
Thiophene-Vinylene-Thiophene-Based Donor-Acceptor Copolymers with Acetylene-Inserted Branched Alkyl Side Chains To Achieve High Field-Effect Mobilities
(2018-11-13)
Chiou, De-Yang
;
Su, Yen-Chen
;
Hung, Kai-En
;
Hsu, Jhih-Yang
;
Hsu, Tze-Gang
2-Alkyl((1))alkyl((2))-type aliphatic side chains with a branching point position at the C-2-position (such as 2-ethylhexyl or 2-octayldodecyl) have been widely implanted into numerous donor-acceptor conjugated copolymers for solution processable transistors or organic solar cells. However, the tertiary branching site located at the second carbon inevitably imposes steric hindrance that twists the main-chain coplanarity and attenuates interchain interactions. In this research, we developed a new two-dimensonal thiophene-vinylene-thiophene (TVT) derivative where a carbon-carbon triple bond is inserted between the thiophene unit and the 2-octyldodecyl group. This acetylene-incorporated TVT (aTVT) was copolymerized with 5,10-di(thiophen-2-yl)naphtho[1,2-c:5,6-c']bis-([1,2,5]thiadiazole) (DTNT) and 5,6-difluoro-4,7-di(thiophen-2-yl[benzo][1,2,5]thiadiazole (DTFBT) to form the polymers PaTVT-NT and PaTVT-FBT, respectively. PTVT-FBT, without the triple bond, was also prepared for comparison. The insertion of a linear triple bond moves the tertiary carbon away from the main chain to reduce the steric hindrance, thereby improving the main-chain coplanarity and facilitating the interchain interactions. The acetylene-incorporated copolymers show better thermal stability, red-shifted absorption spectra, stronger intermolecular aggregation, lower-lying electron affinity, and much higher solid-state crystallinity. Due to the linear and coplanar polymeric backbone supported by theoretical calculation, PaTVT-NT exhibits high crystallinity and adopts strong stacking with an edge-on orientation in the thin film evidenced by 2D-GIXRD, leading to a high p-type OFET mobility up to 1.27 cm(2) V-1 s(-1) with an on-off ratio of 9.22 X 10(5). This value represents the highest value among the NT-based polymers. PaTVT-FBT also achieved a high mobility of 0.78 cm(2) which greatly outperforms the corresponding nonacetylene PTVT-FBT counterpart. Most importantly, the preparation of 2-alkyl((1))alkyl((2))-acetylenyl side chain is synthetically feasible, which can be easily applied to create new conjugated polymers for high-performance solution-processable optoelectronics.