Synthesis and Structure of 2,5,8-Triazido-s-Heptazine: An Energetic and Luminescent Precursor to Nitrogen-Rich Carbon Nitrides
- 9 April 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (17), 5372-5373
- https://doi.org/10.1021/ja048939y
Abstract
Derivatized s-triazine (C3N3) precursors have seen significant recent use in the production of carbon nitride materials. Larger polycyclic molecular precursors, such as those containing an s-heptazine core (C6N7 or tri-s-triazine), may improve stability and order in carbon nitride products. In this Communication, we describe the synthesis and crystal structure of 2,5,8-triazido-s-heptazine (2). Synthesis of 2 was achieved from melon, an oligomeric s-heptazine synthesized by the pyrolysis of NH4SCN. Melon was converted to molecular 2,5,8-trichloro-s-heptazine, which was then transformed to the triazide upon reaction with (CH3)3SiN3. The crystal structure of 2 verifies that the s-heptazine is planar and the azides adopt a pinwheel-like C3h arrangement around the periphery. The s-heptazine core shows π delocalization in the C−N bonds around the periphery (av. 1.33 Å), while the internal planar C−N bonds are longer (1.40 Å). The heptazine units pack into parallel, but offset, layered sheets in the crystal. The triazide 2 exhibits photoluminescence at 430 nm and rapidly and exothermically decomposes upon heating at 185 °C to produce a tan thermally stable carbon nitride powder with a formula near C3N4.Keywords
This publication has 16 references indexed in Scilit:
- Toward Highly Active Two-Photon Absorbing Liquids. Synthesis and Characterization of 1,3,5-Triazine-Based Octupolar MoleculesChemistry of Materials, 2003
- Computation of Aromatic C3N4 Networks and Synthesis of the Molecular Precursor N(C3N3)3Cl6Chemistry – A European Journal, 2003
- Melem (2,5,8-Triamino-tri-s-triazine), an Important Intermediate during Condensation of Melamine Rings to Graphitic Carbon Nitride: Synthesis, Structure Determination by X-ray Powder Diffractometry, Solid-State NMR, and Theoretical StudiesJournal of the American Chemical Society, 2003
- Tri-s-triazine derivatives. Part I. From trichloro-tri-s-triazine to graphitic C3N4 structuresPart II: Alkalicyamelurates M3[C6N7O3], M = Li, Na, K, Rb, Cs, manuscript in preparation.New Journal of Chemistry, 2002
- Synthesis of Nitrogen-Rich Carbon Nitride Networks from an Energetic Molecular Azide PrecursorChemistry of Materials, 2000
- Powder Synthesis and Characterization of Amorphous Carbon NitrideChemistry of Materials, 2000
- Electroluminescence from a new distyrylbenzene based triazine dendrimerJournal of Materials Chemistry, 2000
- Synthesis of Molecular Precursors to Carbon−Nitrogen−Phosphorus Polymeric SystemsChemistry of Materials, 1998
- 1,3,5-TriazinesPublished by Elsevier ,1984
- Preparation and reaction of metal-ketene complexes of zirconium and titaniumJournal of the American Chemical Society, 1982