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Control of Crystallinity of Vinylene-Linked Two-Dimensional Conjugated Polymers by Rational Monomer Design.

ABSTRACT: The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp² -carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylene-quinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylene-vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C-C single bond formation.

SUBMITTER: Pastoetter DL

PROVIDER: S-EPMC9314868 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Synthesis of Vinylene-Linked Two-Dimensional Conjugated Polymers via the Horner-Wadsworth-Emmons Reaction.

Project description:In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D-PPQV1 and 2D-PPQV2, via the Horner-Wadsworth-Emmons (HWE) reaction of C2 -symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4'-bis(diethylphosphonomethyl)biphenyl with C3 -symmetric 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino[2,3-a:2',3'-c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C-C single bond formation for the synthesis of crystalline 2D CPs. Powder X-ray diffraction (PXRD) studies and nitrogen adsorption-desorption measurements demonstrate the formation of proclaimed crystalline, dual-pore structures with surface areas of up to 440 m2 g-1 . More importantly, the optoelectronic properties of the obtained 2D-PPQV1 (Eg =2.2 eV) and 2D-PPQV2 (Eg =2.2 eV) are compared with those of cyano-vinylene-linked 2D-CN-PPQV1 (Eg =2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, Eg =2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction.

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| S-EPMC6641954 | biostudies-literature

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| S-EPMC10964203 | biostudies-literature

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Project description:In recent decade, conjugated microporous polymers (CMPs) were treated as one of the superior porous materials for CO2 uptake. Herein, we prepared two azo-linked CMPs namely: azo-carbazole (Azo-Cz) and azo-phenothiazine (Azo-Tz) from the reduction of the corresponding nitro monomers using sodium borohydride (NaBH4). The obtained polymers were well characterized using many spectroscopic techniques. According to TGA and BET analyses, our CMPs owned good specific surface areas (reaching 315 m2 g–1), and a significant thermal stability. It is also possessed pore sizes of 0.79 and 1.18 nm, respectively, and a reasonable char yields (max. 46 %). Based on CO2 uptake measurements, the CO2 adsorption capacities of these CMPs were very good: up to 40 and 94 mg g–1 at the experiment temperatures 298 and 273 K, respectively. The great CO2 uptake is due to high surface areas that facilitate powerful interactions with CO2 molecules. Supplementary information The online version contains supplementary material available at 10.1007/s10965-021-02803-8.

| S-EPMC8540882 | biostudies-literature

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