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Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

ABSTRACT: The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the C=C-bond-forming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethylcyclopentadienyl) is the most efficient, affording PAVs from a series of bis(alkoxycarbonyldiazomethyl)aromatic compounds with a high trans-C=C-forming selectivity of up to 90%. A PAV sample with a fluorenylene framework as an arylene moiety prepared by the Ru catalyst exhibited a hole mobility of 4 × 10-6 cm2 V-1 s-1.

SUBMITTER: Shimomoto H

PROVIDER: S-EPMC7081273 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

Shimomoto Hiroaki H Moriya Taka-Aki TA Mori Takeshi T Itoh Tomomichi T Kanehashi Shinji S Ogino Kenji K Ihara Eiji E

ACS omega 20200304 10

The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the C=C-bond-forming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethy ...[more]

PMID: 32201764

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Project description:Vinylene-linked two-dimensional conjugated covalent organic frameworks (V-2D-COFs), belonging to the class of two-dimensional conjugated polymers, have attracted increasing attention due to their extended π-conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)-substituted V-2D-COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN-substituted V-2D-COFs via the combination of Knoevenagel polycondensation and water-assisted dynamic Michael-addition-elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high-temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael-addition can proceed the Michael-elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael-addition-elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael-addition-elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN-substituted V-2D-COFs with high crystallinity, as demonstrated by four examples of V-2D-COF-TFPB-PDAN, V-2D-COF-TFPT-PDAN, V-2D-COF-TFPB-BDAN, and V-2D-COF-HATN-BDAN, based on the simulated and experimental powder X-ray diffraction (PXRD) patterns as well as N2 -adsorption-desorption measurements. Moreover, high-resolution transmission electron microscopy (HR-TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V-2D-COFs.

Dataset Information

Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

Publications

Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

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