BF3·Et2O-mediated Friedel–Crafts C–H bond polymerization to synthesize π-conjugation-interrupted polymer semiconductors

Liu, Zhengdong; Chang, Yong-Zheng; Ou, Changjin; Lin, Jinyi; Xie, Linghai; Yin, Changlong; Yi, Ming-Deng; Qian, Yan; Shi, Nai; Huang, Wei

doi:10.1039/c1py00203a

Cited by 31 publications

(25 citation statements)

References 24 publications

(25 reference statements)

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“…Aer the polymerization process the two networks will have the same carbazole-spacer-carbazole backbone. 21 The integration of a thiophene unit into the main structure can increase the polymerization branches from four to ve, and the a-electron rich position of thiophene also can improve the degree of crosslinking through the high oxidative coupling reactivity. Meanwhile, the carbonyl of uorenone was converted into a tertiary alcohol group, which is benecial for CO 2 adsorption.…”

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confidence: 99%

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Qiao

Yang

2014

J. Mater. Chem. A

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Two novel conjugated microporous networks, P-1 and P-2, with carbazole-spacer-carbazole topological model structures, were designed and prepared by FeCl 3 oxidative coupling polymerization. Monomer m-1 (fluorenone spacer) was modified with a thiophene Grignard to form the fluorenyl tertiary alcohol monomer m-2, and this step can increase the polymerization branches from four to five and incorporate the polar -OH group into the building block. N 2 adsorption isotherms show that, after modification, the Brunauer-Emmett-Teller (BET) surface area of P-2 (1222 m 2 g À1) is two times that of P-1 (611 m 2 gand the total pore volume increases 1.63 times from 0.95 to 1.55 at P/P 0 ¼ 0.99. However, the domain pore size (centred at 1.19 nm) and the pore distribution of both networks are not changed. It demonstrates that the domain pore width may be determined by the size of the rigid carbazole-spacercarbazole backbone, not the degree of crosslinking when the networks were prepared under same polymerization conditions in this system. Hydrogen physisorption isotherms of P-1 and P-2 show that the H 2 storage can be up to 1.05 wt% and 1.66 wt% at 77 K and 1.1 bar, and the isosteric heat is 9.89 kJ mol À1 and 10.86 kJ mol À1 , respectively. At 273 K and 1.1 bar, the CO 2 uptake capacity of P-2 can be up to 14.5 wt% which is 1.63 times that of P-1 under the same conditions. The H 2 and CO 2 uptake capacities of P-2 are among the highest reported for conjugated microporous networks under similar conditions. The CO 2 /CH 4 and CO 2 /N 2 selectivity results indicate that P-1 exhibits a slightly higher separation ability than P-2. There is often a trade-off between absolute uptake and selectivity in other microporous organic polymers. Fine design and tailoring the topological structure of the monomer can change the adsorption isosteric enthalpy and optimize the gas uptake performance. The obtained networks with the carbazole-spacer-carbazole rigid backbone show promise for potential use in clean energy applications and the environmental field.

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confidence: 99%

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Qiao

Yang

2014

J. Mater. Chem. A

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“…The active CIHP material, i.e., PCzPF, was synthesized via a BF 3 ·Et 2 O‐mediated Friedel–Crafts CH bond polymerization method. [ 17 ] Moreover, a CIHP derivative, i.e., poly[9‐(4‐(octyloxy)phenyl)‐2‐(3‐(9‐phenyl‐9 H ‐fluoren‐9‐yl)‐9 H ‐carbazol‐9‐yl)‐9H‐fluoren] (PCzPF‐PF) was synthesized via BF 3 ·Et 2 O‐catalyzed Friedel–Crafts reaction (Figure 1b). Owing to their long alkyl chain and hyperbranched structure, both of the PCzPF and PCzPF‐PF showed good solubility in most organic solvents, such as chloroform, dichloromethane, and https://dichlorobenzene.…”

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confidence: 99%

Flexible Metal‐Free Memory Electronic Made of π‐Conjugation‐Interrupted Hyperbranched Polymer Switch and Reduced Graphene Oxide Electrodes

Liu

Song

Yin

et al. 2020

Macro Materials & Eng

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A flexible metal‐free flash memory device with reduced graphene oxide films as electrodes and diarylfluorene‐based π‐conjugation‐interrupted hyperbranched polymers (CIHPs) as active switches is reported. Two CIHPs, named PCzPF and PCzPF‐PF, are synthesized via BF3•Et2O‐catalyzed fluorenol’s Friedel–Crafts reaction, where the PCzPF‐PF is designed by the decoration of hindrance functional groups, i.e., bulky 9‐phenyl‐fluorenyl (PF) moieties, at the end‐groups of PCzPF. Both of the two CIHPs exhibit excellent solubility and thermal stability. The PCzPF‐based device exhibits no switching effect while the PCzPF‐PF‐based device shows a flash type memory effect, indicating the incorporation of PF groups plays a critical role in realizing electrically bistable behaviors. In particular, the optimized memory exhibits a high ON/OFF ratio of > 3.0 × 103, long retention time of up to 1.2 × 104 s, and high mechanical stability. This work opens a new avenue for metal‐free memory electronics through a low‐cost and full‐solution process approach.

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“…In order to alleviate some of these problems, exploring new polymerization methods to synthesize polycyclopentadithiophenes may lead to new possibilities for these intriguing materials . BF 3 ·Et 2 O catalyzed Friedel–Crafts self‐condensation polymerization of AB x ( x ≥ 2) ‐type tertiary alcohols is a non‐metal catalyst and atom‐economical polymerization . It can carry out under mild reaction conditions to prepare branched polymers with only water as the byproduct .…”

Section: Introductionmentioning

confidence: 99%

Cyclopentadithiophene based branched polymer electrets synthesized by friedel–crafts polymerization

Liu

Bao

Ling

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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In this report, the BF 3 ÁEt 2 O catalyzed Friedel-Crafts polymerization of cyclopentadithiophene monomers for branched conjugation-interrupted polymer electrets with the potential application in OFET memories were demonstrated. Branched polycyclopentadithiophenes with controlled molecular weights (M n ) of approximately 8800 g/mol and narrow polydispersity index (PDI 5 1.08-1.49) were obtained through the optimized polymerization temperature and time, and monomer addition strategy. OFET memories by using the synthesized polymers as the electret layers were fabricated and exhibited multilevel flash memory behaviors, wide memory windows, high on/off ratios, and long retention lifetime. Impressively, due to the strong hydrophobic, extended pi-conjugation and electron-donating properties, the branched polycyclopentadithiophene based OFET memory exhibited much lower programming voltage than other branched polymer electrets based devices. It is expected that the branched polycyclopentadithiophenes probably have potential application in other organic electronic devices.

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BF3·Et2O-mediated Friedel–Crafts C–H bond polymerization to synthesize π-conjugation-interrupted polymer semiconductors

Cited by 31 publications

References 24 publications

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Flexible Metal‐Free Memory Electronic Made of π‐Conjugation‐Interrupted Hyperbranched Polymer Switch and Reduced Graphene Oxide Electrodes

Cyclopentadithiophene based branched polymer electrets synthesized by friedel–crafts polymerization

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