Viewpoint 10 — An application of quantum chemistry to the search for new materials: metastable polymers formed at high pressures

• Published in: Journal of molecular structure. Theochem 1993, Vol.284 (3), p.299-306
• Main Author: Jones, Walter H.
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Inorganic and organomineral polymers; Physicochemistry of polymers; Properties and characterization
• ISSN: 0166-1280; 1872-7999
• DOI: 10.1016/0166-1280(93)87011-2

MNDO/AM1 studies indicate the possibility of forming metastable polymers of nitrogen oxides, through application of the extreme pressures which have become accessible in recent years. Kinetically stable open-chain polymers of nitric oxide, (NO) x , analogous to the known polythiazyl, (SN) x , and/or (ONNO) x , and polycyclic (ONNO) x, may be obtainable. Of particular interest is the possibility of forming a planar, cis, trans open-chain polymer of nitrous oxide, which is geometrically quite similar to (SN) x . As offshoots of the investigations, it is found that: (1) a polycyclic derivative, (SNNS) x , may be formed exothermically from (SN) x and possess superior conducting properties; (2) marriage of a hypothetical cyclic trimer of nitric oxide and an open-chain polymer of nitrous oxide may account for experimental investigations which have reported a preponderance of the (NO) 3(ONN) x + cations in mass-spectrometric studies of mixtures of nitric and nitrous oxides; (3) an interesting series of strain-free cage compounds, N 6O 6, N 6S 6, and N 12H 6, which are isostructural with the skeleton of the known hydrocarbon iceane, C 12H 18, may be realizable; (4) high-energy cyclic oligomers of nitrous oxide, (N 2O) 2–6, which are similar to crown ethers, and whose derivatives might form a novel series of sequestering agents or gas generators, are possible.