From Linear Molecular Chains to Extended Polycyclic Networks: Polymerization of Dicyanoacetylene

Gou, Huiyang; Zhu, Li; Huang, Haw Tyng; Biswas, Arani; Keefer, Derek W.; Chaloux, Brian L.; Prescher, Clemens; Yang, Lechen; Kim, Duck Young; Ward, Matthew D.; Lerach, Jordan O.; Wang, Shengnan; Oganov, Artem R.; Epshteyn, Albert; Badding, John V.; Strobel, Timothy A.

doi:10.1021/acs.chemmater.7b01446

Cited by 10 publications

(16 citation statements)

References 120 publications

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“…, irradiation) to initiate reactivity. , Recently, much interest has been shown to various organic molecules subjected to high pressures, where solid-state reactions readily take place. Here, novel reaction pathways become accessible and previously unrealized metastable materials may be synthesized simply through compression. − …”

Section: Introductionmentioning

confidence: 99%

Evidence for Functionalized Carbon Nanothreads from π-Stacked, para-Disubstituted Benzenes

Tang

Strobel

2020

J. Phys. Chem. C

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Recent studies of highly compressed organic molecules reveal the synthesis of one-dimensional (1D) nanothread structures, typically formed through addition reactions of unsaturated bonds. Although these nanostructures have been demonstrated from molecules such as benzene, pyridine, and thiophene, it remains unclear whether functionalized nanothreads can be produced from precursors with different substituent groups under high-pressure conditions. Here, we examine the controlled pressure-induced polymerization of several para-disubstituted benzene molecular crystals and cocrystals with different functional groups including dinitrobenzene, diethynylbenzene, and dicyanobenzene. X-ray diffraction and infrared spectroscopy provide evidence for the formation of ordered nanostructures that maintain their topological relationship with the starting molecular phase and preserve initial functionality. Although no clear correlation between specific functional groups and polymerization pressure was observed, the proximity toward sandwich-type π-stacking within the starting molecular crystals influences reaction pathway selectivity and the formation of new saturated bonds under normal compression conditions. We propose a simple correlation related to π-stacking, wherein the stacking distance between parallel planes of monomers and the slippage angle between π-stacks are important aspects that influence polymerization pathway selectivity and the formation of ordered products under normal compression at room temperature. Functionalized nanothread structures are possible through careful precursor selection, and an improved understanding of π-stacking polymerization may lead to the realization of well-defined organic nanostructures with designed functionality.

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Section: Introductionmentioning

confidence: 99%

Evidence for Functionalized Carbon Nanothreads from π-Stacked, para-Disubstituted Benzenes

Tang

Strobel

2020

J. Phys. Chem. C

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“…Fourier transform IR (FTIR) spectra of HPHT-C 3 N 3 P (Figure S2) indicate the absence of both amine groups (usually present in C 3 N 4 -related materials from melamine-containing precursors) and adsorbed water molecules/surface hydroxyl groups. The HPHT-C 3 N 3 P sample exhibits several broad IR absorption bands between ∼800 and 1600 cm –1 , which are different from the vibrational frequencies of the P(CN) 3 starting material, but similar to C 3 N 4 -related materials including amorphous C 3 N 3 PO 1– x and “triazine-based graphitic carbon nitride” (TGCN). ,,− The lower-frequency absorptions are also consistent with phenyl-phosphorus stretching modes as in P(C 6 H 5 ) 3 compounds . On the basis of the observed vibrational modes, the basic local structure of HPHT-C 3 N 3 P is inferred to be P-bridged heteroatomic C–N rings.…”

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confidence: 62%

Modifying Carbon Nitride through Extreme Phosphorus Substitution

Wang

Gou

Zhu

et al. 2019

ACS Materials Lett.

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A glassy carbon phosphonitride material with bulk chemical composition roughly approximating C3N3P was synthesized through a high-pressure, high-temperature process using a pure P(CN)3 molecular precursor. The resulting material (hereafter referred to as “HPHT-C3N3P”) was characterized using a variety of techniques, including X-ray scattering, pair distribution function analysis, 31P, 13C, 15N magic-angle spinning nuclear magnetic resonance spectroscopies; X-ray photoelectron spectroscopy, and Raman and IR spectroscopies. The measurements indicate that HPHT-C3N3P lacks long-range structural order with a local structure predominantly composed of a sp2, s-triazine-like network in which phosphorus atoms substitute for bridging nitrogen sites found in related C3N4 materials. The HPHT-C3N3P sample exhibits semiconducting properties, with electrical transport dominated by variable-range hopping. The high phosphorus content of HPHT-C3N3P (approaching 13 at. %) is associated with a major decrease in the optical absorption edge (∼0.4 eV) and a ∼1010-fold increase in electrical conductivity, as compared to previously-reported P-doped graphitic g-C3N4 (0.6-3.8 at. % P). The HPHT-C3N3P sample is considerably harder than layered g-C3N4 and exhibits superior thermal stability up to ∼700 °C in air. These results demonstrate a remarkable range of tunable properties possible for C3N4-related materials through elemental substitution and provide valuable information to guide the design of new materials.

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“…The structure containing the amino groups is ready to eliminate ammonia gas at appropriate conditions. Besides HCN and CH 3 CN, other nitriles like cyanogen [120], tetracyanoethylene (TCNE) [121], phosphorous tricyanide (P(CN) 3 ) [122], tetracyanomethane (C(CN) 4 ) [123] and dicyanoacetylene [124] also polymerize under high pressure.…”

Section: Nitrilesmentioning

confidence: 99%

From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds

Yang

Wang

et al. 2019

Crystals

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With the development of high-pressure apparatus, in situ characterization methods and theoretical calculations, high-pressure technology becomes a more and more important method to synthesize new compounds with unusual structures and properties. By compressing compounds containing unsaturated carbon atoms, novel poly-ionic polymers, graphanes and carbon nanothreads were obtained. Their compositions and structures were carefully studied by combining multiple cutting-edge technologies, like the in situ high-pressure X-ray and neutron diffraction, transmission electron microscopy, pair distribution function, solid-state nuclear magnetic resonance and gas chromatography-mass spectroscopy. The reaction mechanisms were investigated based on the crystal structure at the reaction threshold pressure (the pressure just before the reaction taking place), the long-range and short-range structure of the product, molecular structure of the intermediates, as well as the theoretical calculation. In this review, we will summarize the synthesis of carbon materials by compressing the unsaturated compounds and its reaction characteristics under extreme conditions. The topochemical reaction mechanism and related characterization methods of the molecular system will be highlighted. This review will provide a reference for designing chemical reaction and exploring novel carbon materials under high-pressure condition.

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From Linear Molecular Chains to Extended Polycyclic Networks: Polymerization of Dicyanoacetylene

Cited by 10 publications

References 120 publications

Evidence for Functionalized Carbon Nanothreads from π-Stacked, para-Disubstituted Benzenes

Evidence for Functionalized Carbon Nanothreads from π-Stacked, para-Disubstituted Benzenes

Modifying Carbon Nitride through Extreme Phosphorus Substitution

From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds

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