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3604732 
Journal Article 
High-Pressure Reactivity of Triptycene Probed by Raman Spectroscopy 
Ray, P; Gray, JL; Badding, JV; Lueking, AD 
2016 
Yes 
Journal of Physical Chemistry B
ISSN: 1520-6106
EISSN: 1520-5207 
120 
42 p.11035-11042 
11035-11042 
English 
27676228 
WOS:000386641500016 
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 sp(3)-hybridized bridgehead carbon sites. At 25 GPa and 298 K, triptycene polymerizes to yield an amorphous hydrogenated carbon, with FTIR indicating an sp(3) 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.