Chemical and phase transformations of thiophene at high pressures

Pruzan, Ph.; Chervin, J. C.; Forgerit, J. P.

doi:10.1063/1.462461

Cited by 28 publications

(24 citation statements)

References 20 publications

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“…Similar irreversible chemical transformations were also observed in thiophene and furan, except that the transformation pressures are lower, i.e., at 16 GPa and 12 GPa, respectively. 3,6 Base on the similar threshold pressure for chemical transformations for benzene and pyridine, i.e., 23 and 22 GPa, it is therefore reasonable to propose that aromatic compounds with similar initial structures may undergo similar pressure-induced transformations.…”

Section: F Discussionmentioning

confidence: 99%

“…1 These compounds have been widely studied in chemical synthesis under elevated temperatures and pressures as the precursors of technological materials, such as conjugated polymers and amorphous solids. [2][3][4][5][6][7][8] In addition, rich structural, chemical, and phase behaviors have been observed in a broad pressure-temperature regions where new optical and thermodynamic properties have been characterized. [9][10][11][12][13][14][15][16] For instance, application of high pressure to benzene resulted in several structural changes and the formation of new compounds, such as crystalline and amorphous graphite materials, depending on the extreme conditions rendered.…”

Section: Introductionmentioning

confidence: 99%

“…13,14 Other aromatic compounds, such as thiophene and furane, were also found to exhibit intriguing pressure-induced structural transformations. 3,6,7 Pyridine ͑C 5 H 5 N͒, a heterocyclic aromatic compound, resembles the well-known benzene structure ͑C 6 H 6 ͒ by replacing one of the CH groups with a nitrogen atom. Isoelectronic to benzene, the structures and properties of pyridine have been extensively investigated by various experimental approaches at ambient pressure, including Raman spectroscopy, [17][18][19][20] infrared ͑IR͒ spectroscopy 17,18,[21][22][23][24] as well as x-ray diffraction.…”

Section: Introductionmentioning

confidence: 99%

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Raman and infrared spectroscopy of pyridine under high pressure

et al. 2010

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We report the structural transitions of pyridine as a function of pressure up to 26 GPa using in situ Raman spectroscopy and infrared absorption spectroscopy. By monitoring changes in the Raman shifts in the lattice region as well as the band profiles in both Raman and IR spectra, a liquid-to-solid transition at 1 GPa followed by solid-to-solid transitions at 2, 8, 11, and 16 GPa were observed upon compression. These transitions were found to be reversible upon decompression from 22 GPa. A further chemical transformation was observed when compressed beyond 22 GPa as evidenced by the substantial and irreversible changes in the Raman and infrared spectra, which could be attributed to the destruction of the ring structure. The observed transformations in pyridine were also compared to those for benzene. The similar transition sequence with well-aligned transition pressures suggests that these isoelectronic aromatics may have similar structures and stabilities under high pressure.

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Section: F Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Raman and infrared spectroscopy of pyridine under high pressure

et al. 2010

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“…28 Ring opening of thiophene at 16 GPa is also corroborated by emergence of saturated CH stretching vibrations. 29 The transition of αto β-pyrazole at 0.45 GPa leads to disordering of H atoms. 30 Phenanthrene still displays some long range order despite it transforms to hydrogenated carbon above 20.0 GPa.…”

Section: Introductionmentioning

confidence: 99%

Effect of pressure on heterocyclic compounds: Pyrimidine and s-triazine

Xiong

et al. 2014

The Journal of Chemical Physics

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We have examined the high-pressure behaviors of six-membered heterocyclic compounds of pyrimidine and s-triazine up to 26 and 26.5 GPa, respectively. Pyrimidine crystallizes in Pna2₁ symmetry (phase I) with the freezing pressure of 0.3 GPa, and transforms to another phase (phase II) at 1.1 GPa. Raman spectra of several compression-decompression cycles demonstrate there is a critical pressure of 15.5 GPa for pyrimidine. Pyrimidine returns back to its original liquid state as long as the highest pressure is below 15.1 GPa. Rupture of the aromatic ring is observed once pressure exceeds 15.5 GPa during a compression-decompression cycle, evidenced by the amorphous characteristics of the recovered sample. As for s-triazine, the phase transition from R-3c to C2/c is well reproduced at 0.6 GPa, in comparison with previous Raman data. Detailed Raman scattering experiments corroborate the critical pressure for s-triazine may locate at 14.5 GPa. That is, the compression is reversible below 14.3 GPa, whereas chemical reaction with ring opening is detected when the final pressure is above 14.5 GPa. During compression, the complete amorphization pressure for pyrimidine and s-triazine is identified as 22.4 and 15.2 GPa, respectively, based on disappearance of Raman lattice modes. Synchrotron X-ray diffraction patterns and Fourier transform infrared spectra of recovered samples indicate the products in two cases comprise of extended nitrogen-rich amorphous hydrogenated carbon (a-C:H:N).

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“…For the two first examples the amorphization is reversible, while for aromatic molecular crystals like benzene 9 or thiophene 10 , an irreversible amorphization is observed under high pressure due to the break of the itinerant bond and the creation of a highly reticulated polymer.…”

Section: Introductionmentioning

confidence: 98%

Mechanism of pressure induced amorphization of SnI4: A combined x-ray diffraction—x-ray absorption spectroscopy study

Fonda

Polian

Shinmei

et al. 2020

The Journal of Chemical Physics

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We have studied the amorphization process of SnI 4 up to 26.8GPa with unprecedented experimental details by combining Sn and I K edge X-ray absorption spectroscopy and powder X-ray diffraction. Standards and reverse Monte Carlo extended X-ray absorption fine structure (EXAFS) refinements confirm that the SnI 4 tetrahedron is a fundamental structural unit that is preserved through the crystalline phase-I to crystalline phase-II transition about 7 to 10GPa and then in the amorphous phase that appears above 20GPa. Up to now unexploited Iodine EXAFS reveals to be extremely informative and confirms the formation of iodine iodine short bonds close to 2.85Å in the amorphous phase at 26.8 GPa. A coordination number increase of Sn in the crystalline phase-II appears to be excluded, while the deformation of the tetrahedral units proceeds through a flattening that keeps the average I-Sn-I angle close to 109.5°. Moreover, we put in evidence the impact of pressure on the Sn near edge structure under competing geometrical and electronic effects.

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Chemical and phase transformations of thiophene at high pressures

Cited by 28 publications

References 20 publications

Raman and infrared spectroscopy of pyridine under high pressure

Raman and infrared spectroscopy of pyridine under high pressure

Effect of pressure on heterocyclic compounds: Pyrimidine and s-triazine

Mechanism of pressure induced amorphization of SnI4: A combined x-ray diffraction—x-ray absorption spectroscopy study

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