Pentiptycene Building Blocks Derived from Nucleophilic Aromatic Substitution of Pentiptycene Triflates and Halides

Kundu, Sandip; Tan, Wei; Yan, Jyu-Lun; Yang, Jye‐Shane

doi:10.1021/jo100812z

Cited by 13 publications

(13 citation statements)

References 54 publications

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“…The synthesis of the three pentiptycene‐derived additives, TA, DA, and TP, is shown in Scheme . The pentiptycene building blocks 3 and 4 were prepared according to the previously reported protocols . The two‐step synthesis of TA from block 3 was recently reported, in which the intermediate 5 was prepared using a typical Buchwald‐Hartwig C–N coupling reaction, and the subsequent reduction of the nitro groups was carried out with Sn(II) chloride in the presence of HCl.…”

Section: Resultsmentioning

confidence: 99%

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Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism

Tan

Lee

Tseng

et al. 2019

J Chinese Chemical Soc

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Despite the long history of polyaniline chemistry, backbone‐substituted polyanilines are limited. Here, we report the synthesis of pentiptycene‐incorporated polyanilines through acidic aniline oxidative polymerization with three pentiptycene derivatives, TA, DA, and TP, as nucleate additives. The reactivity of TA > DA ≫ TP, as evidenced by structural and property analysis of the corresponding polyaniline products, demonstrates a radical coupling mechanism and the formation of Dewar π‐complex intermediates for the chain propagation. In addition, the iptycene substituent effect on enhancing the electrochemical stability and charge storage capability of polyaniline are discussed with a clip model, namely, the threading of neighboring polyaniline chains through the U‐ and V‐shaped cavities of pentiptycene restricts lateral motions of the polymer chains and promotes interchain conductivity. Density function theory (DFT) calculations suggest a larger clipping effect for the U versus V cavities. Both the conclusion of a terminal planar p‐phenylenediamine (ppda) group being the key component of an effective nucleate and the concept of interchain clipping for enhanced electrochemical performance should facilitate the design and synthesis of novel polyanilines for electronic applications.

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Section: Resultsmentioning

confidence: 99%

“…Solvents for electrochemical measurements were HPLC grade. The synthesis of compounds 3 , 4 ,, 5 , and TA was previously reported. Typical synthetic procedures and characterization data for new compounds are shown in the following.…”

Section: Methodsmentioning

confidence: 99%

Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism

Tan

Lee

Tseng

et al. 2019

J Chinese Chemical Soc

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“…Aminopentiptycene 8 was prepared from compound 6 in two steps via intermediate 7 by Pd‐catalyzed coupling with 1‐octyne, followed by hydrogenation to simultaneously reduce the nitro and alkynyl groups into amino and alkyl groups, respectively. Both compounds 3 and 6 are known pentiptycene building blocks that contain functional groups in the central ring 34. Because all of the condensation reactions provided the E configuration of the azobenzene, the corresponding Z isomers were prepared by irradiation of the E isomers in n ‐hexane or CH 2 Cl 2 at 365 nm, and mixtures of E and Z isomers that contained 66–78 % of the Z isomers were obtained.…”

Section: Resultsmentioning

confidence: 99%

“…The syntheses of compounds 1O R, 3, 6,and 10 have been reported previously. [20,34] GeneralP rocedure for the Synthesis of Pentiptycene-Incorporated Azobenzenes Compound 5,8,o r10 was added to af reshly prepared solution of compound 9 in EtOAc and acetic acid (10 mL, 1:1v/v) and the mixture was stirred for 4h.T he solvents were removed under vacuum and purified by column chromatography on silica gel (CH 2 Cl 2 /nhexane, 3:1) to afford the target compounds (E-2NR, E-2R,a nd 11, respectively) as ared solid.…”

Section: Methodsmentioning

confidence: 99%

Light‐Gated Molecular Brakes Based on Pentiptycene‐Incorporated Azobenzenes

Tan

Chuang

Chen

et al. 2015

Chemistry An Asian Journal

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Three azobenzene derivatives (2 R, 2 OR, and 2 NR) that differed in their terminal substituent (alkyl, alkyloxy, and dialkylamino, respectively) have been synthesized and investigated as molecular brakes, in which the rigid H-shaped pentiptycene group functioned as a rotor and the dinitrophenyl group as a "brake pad". The E and Z isomers of these compounds corresponded to the "brake-off" and "brake-on" states, respectively. The rotation rate of the rotor was evaluated by VT NMR spectroscopy for the brake-on state and by DFT calculations for the brake-off state. The difference between the rotation rates for the rotor in the two states was as large as eight orders of magnitude at ambient temperature. Photochemical switching of the azobenzene moieties afforded efficiencies of 55-67%. A combination of photochemical E→Z and thermal Z→E isomerization promoted the switching efficiency up to 78%. The terminal substituent affected both the photochemical and thermal switching efficiencies. Solvent polarity also played an important role in the lifetimes of the Z isomers. These azobenzene systems displayed similar braking powers but superior switching efficiencies to the stilbene analogue (1O R; ca. 60% vs 20%).

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“…The synthesis of compound 1 has been reported. 4 All the solvents and reagents for synthesis were reagent grade and used as received unless otherwise stated. Aniline was distilled with zinc dust under reduced pressure and stored at 4°C in brown bottles in inert atmosphere before use.…”

Section: Materials and Synthesismentioning

confidence: 99%

Iptycene substitution enhances the electrochemical activity and stability of polyanilines

et al. 2018

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The electrochemical stability of polyaniline (PANI) films is a key issue for their application as electrode materials. This work demonstrates that a low fraction (<5%) of pentiptycene incorporation of the PANI conjugated backbone could significantly enhance the capacitive performance and charge-discharge cycling stability of PANI films, attributable to the clipping effect of pentiptycene cavities that restricts motional freedom of polymer chains and promotes interchain conductivity.

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Pentiptycene Building Blocks Derived from Nucleophilic Aromatic Substitution of Pentiptycene Triflates and Halides

Cited by 13 publications

References 54 publications

Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism

Additive‐dependent iptycene incorporation in polyanilines: Insights into the pentiptycene clipping effect and the polymerization mechanism

Light‐Gated Molecular Brakes Based on Pentiptycene‐Incorporated Azobenzenes

Iptycene substitution enhances the electrochemical activity and stability of polyanilines

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