High-Pressure Reactivity of Triptycene Probed by Raman Spectroscopy

Paramita Ray, Jennifer Lynn Gray, John V. Badding, Angela Lueking

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The high-pressure reactivity of caged olefinic carbons and polyatomic aromatic hydrocarbons (PAHs) are of interest because of their ability to produce unique C-H networks with varying geometries and bonding environments. Here, we have selected triptycene to explore the creation of pores via high-pressure polymerization. Triptycene has internal free volume on a molecular scale that arises due to its paddle wheel-like structure, formed via fusion of three benzene rings via sp3-hybridized bridgehead carbon sites. At 25 GPa and 298 K, triptycene polymerizes to yield an amorphous hydrogenated carbon, with FTIR indicating an sp3 C-H content of approximately 40%. Vibrational spectroscopy conclusively demonstrates that triptycene polymerizes via cycloaddition reactions at the aromatic sites via a ring opening mechanism. The bridgehead carbons remain intact after polymerization, indicating the rigid backbone of the triptycene precursor is retained in the polymer, as well as molecular-level (∼1-3 Å) internal free volume. High resolution transmission electron microscopy, combined with dark field imaging, indicates the presence of ∼10 nm voids in the polymer, which we attribute to either polymeric clustering or a hierarchical tertiary porous network. Creation of a polymerized network that retains internal voids via high-pressure polymerization is attributed to the presence and retention of the bridgehead carbons.

Original languageEnglish (US)
Pages (from-to)11035-11042
Number of pages8
JournalJournal of Physical Chemistry B
Volume120
Issue number42
DOIs
StatePublished - Oct 27 2016

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Raman spectroscopy
Carbon
reactivity
carbon
polymerization
Free volume
Polymerization
voids
Polymers
paddles
Aromatic Hydrocarbons
Vibrational spectroscopy
Cycloaddition
Aromatic hydrocarbons
rings
polymers
cycloaddition
High resolution transmission electron microscopy
wheels
Benzene

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Ray, Paramita ; Gray, Jennifer Lynn ; Badding, John V. ; Lueking, Angela. / High-Pressure Reactivity of Triptycene Probed by Raman Spectroscopy. In: Journal of Physical Chemistry B. 2016 ; Vol. 120, No. 42. pp. 11035-11042.
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High-Pressure Reactivity of Triptycene Probed by Raman Spectroscopy. / Ray, Paramita; Gray, Jennifer Lynn; Badding, John V.; Lueking, Angela.

In: Journal of Physical Chemistry B, Vol. 120, No. 42, 27.10.2016, p. 11035-11042.

Research output: Contribution to journalArticle

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