Tuning of gallery heights in a crystalline 2D carbon nitride network

Chong, Samantha Y ORCID: 0000-0002-3095-875X, Jones, James TA, Khimyak, Yaroslav Z, Cooper, Andrew I ORCID: 0000-0003-0201-1021, Thomas, Arne, Antonietti, Markus and Bojdys, Michael J (2013) Tuning of gallery heights in a crystalline 2D carbon nitride network. JOURNAL OF MATERIALS CHEMISTRY A, 1 (4). pp. 1102-1107. ISSN 2050-7488, 2050-7496

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Abstract

Poly(triazine imide) - a 2D layered network - can be obtained as an intercalation compound with halides from the ionothermal condensation of dicyandiamide in a eutectic salt melt. The gallery height of the intercalated material can be tuned via the composition of the eutectic melt and by post-synthetic modification. Here, we report the synthesis of poly(triazine imide) with intercalated bromide ions (PTI/Br) from a lithium bromide and potassium bromide salt melt. PTI/Br has a hexagonal unit-cell (P6<inf>3</inf>cm (no. 185); a = 8.500390(68) Å, c = 7.04483(17) Å) that contains two layers of imide-bridged triazine (C<inf>3</inf>N<inf>3</inf>) units stacked in an AB-fashion as corroborated by solid-state NMR, FTIR spectroscopy and high-resolution TEM. By comparison with a recently reported material PTI/Li ⁺Cl^-, prepared from a LiCl/KCl eutectic, the layer-stacking distance in the analogous bromide material was expanded from 3.38 Å to 3.52 Å-an exceptionally large spacing for an aromatic, discotic system (cf. graphite 3.35 Å). Subsequent treatment of PTI/Br with concentrated ammonium fluoride yields poly(triazine imide) with intercalated fluoride ions (PTI/F) (P6<inf>3</inf>/m (no. 176); a = 8.4212(4) Å, c = 6.6381(5) Å) as a statistical phase mix with PTI/Br. Fluoride intercalation leads to a contraction of the gallery height to 3.32 Å, demonstrating that the gallery height is synthetically tuneable in these materials. © The Royal Society of Chemistry 2013.

Item Type:	Article
Additional Information:	## TULIP Type: Articles/Papers (Journal) ##
Uncontrolled Keywords:	40 Engineering, 3403 Macromolecular and Materials Chemistry, 4016 Materials Engineering, 34 Chemical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	18 Feb 2015 11:10
Last Modified:	06 Jun 2025 02:56
DOI:	10.1039/c2ta01068b
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/2007108