Synthesis of Conjugated Copolymer Containing Spirobifluorene Skeleton by Acyclic Diene Metathesis Polymerization for Polymer Light‐Emitting Diode Applications

Abstract

Grubbs‐type, Hoveyda‐type, cyclic alkyl amino carbene (CAAC)‐based ruthenium olefin metathesis catalysts were used for the acyclic diene metathesis (ADMET) polymerization of 2,7‐divinyl‐9,9‐di‐n‐octylfluorene (DVF). Additionally, various ratios of DVF and 2,2′,7,7′‐tetravinyl‐9,9′‐spirobifluorene (TVSF) were subjected to ADMET polymerization to obtain polymers P1–P7. Polymers P1–P4 were analyzed with gel permeation chromatography, UV–vis spectroscopy, and photoluminescence spectroscopy. As the TVSF ratio increases, polymers exhibit lower solubility but a narrower band in the photoluminescence spectrum. Polymer light‐emitting diode (PLED) devices were fabricated with polymers P1, P2, and P3. The performances of the PLED devices indicated that polymers including more spirobifluorene blocks showed better turn‐on voltage, brightness, current efficiency, and power efficiency.

Recent Advances in the Domain of Cyclic (Alkyl)(Amino) Carbenes

“…[68] Hong et al applied Grubbs-type and Hoveyda-type, cAAC stabilized ruthenium catalysts for olefin metathesis of 2,7divinyl-9,9-di-noctylfluorene (18) and 2,2',7,7'-tetravinyl-9,9'-spirobifluorene (19) in different ratios to synthesize seven copolymerization products in good to excellent yields (Scheme 7). [69] The copolymers with spirobifluorene units are better for polymer Light-Emitting Diode (LED) devices and display improved performance like better turn-on voltage, brightness, current, and power efficiency. Morvan et al have summarized cAACÀ Ru catalyzed olefin metathesis in a recent review.…”

“…cAACs have not only been used to synthesize nucleophilic organoboron compounds but also in the stabilization of neutral boronmonochloride (66), boryl anion (67), [135] aluminum radicals (68) [136] as well as radical cations (69). Braunschweig and coworkers have reported the synthesis of a neutral cAACstabilized boron-containing radical.…”

Synthesis of air‐stable poly(benzonorbornadiene)s via ring‐opening metathesis polymerization

“…and Ru-catalyzed metathesis polymerizations 12,[23][24][25][26] are the representative polymerizations to afford functional polymers with high functional group tolerance in mild conditions. Recently, highly functionalized polymers with structural advantages are reported by using various transition-metal catalysts such as controlled synthesis of helical polymers, [27][28][29][30][31] brush polymers, 32 polyallenes, 33 and polycarbenes.…”

“…Transition‐metal mediated polymerizations provide big advances in polymer science and industrial field. Precisely controlled polymerization techniques have been developed by using various transition‐metals, and Cu‐catalyzed atom transfer radical polymerizations (ATRPs) 18–22 and Ru‐catalyzed metathesis polymerizations 12,23–26 are the representative polymerizations to afford functional polymers with high functional group tolerance in mild conditions. Recently, highly functionalized polymers with structural advantages are reported by using various transition‐metal catalysts such as controlled synthesis of helical polymers, 27–31 brush polymers, 32 polyallenes, 33 and polycarbenes 34 …”

Research progress on spirofluorene-based closed-loop compounds

“…此外, 这类分子通常具有比较强的光学活性, 常被用来 制作光学器件 [27,28] . 不仅如此, 部分环状大分子具有构 象多样性 [29] , 利用"构象选择"机理可以使其作为分子 识别的重要工具.…”