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Article

Vibrational Analysis of Benziodoxoles and Benziodazolotetrazoles

Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275, USA
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Author to whom correspondence should be addressed.
Academic Editors: Sergei Manzhos and Jacinto Sá
Received: 27 March 2021 / Revised: 27 April 2021 / Accepted: 5 May 2021 / Published: 14 May 2021
(This article belongs to the Special Issue Physical Chemistry Perspectives for the New Decade)
Tetrazoles are well known for their high positive enthalpy of formation which makes them attractive as propellants, explosives, and energetic materials. As a step towards a deeper understanding of the stability of benziodazolotetrazole (BIAT)-based materials compared to their benziodoxole (BIO) counterparts, we investigated in this work electronic structure features and bonding properties of two monovalent iodine precursors: 2-iodobenzoic acid and 5-(2-iodophenyl)tetrazole and eight hypervalent iodine (III) compounds: I-hydroxybenzidoxolone, I-methoxybenziodoxolone, I-ethoxybenziodoxolone, I-iso-propoxybenziodoxolone and the corresponding I-hydroxyben ziodazolotetrazole, I-methoxybenziodazolotetrazole, I-ethoxybenziodazolotetrazole and I-iso- propoxybenziodazolotetrazole. As an efficient tool for the interpretation of the experimental IR spectra and for the quantitative assessment of the I−C, I−N, and I−O bond strengths in these compounds reflecting substituent effects, we used the local vibrational mode analysis, originally introduced by Konkoli and Cremer, complemented by electron density and natural bond orbital analyses. Based on the hypothesis that stronger bonds correlate with increased stability, we predict that, for both series, i.e., substituted benziodoxoles and benziodazolotetrazoles, the stability increases as follows: I-iso-propoxy < I-ethoxy < I-methoxy < I-hydroxy. In particular, the I−N bonds in the benziodazolotetrazoles could be identified as the so-called trigger bonds being responsible for the initiation of explosive decomposition in benziodazolotetrazoles. The new insight gained by this work will allow for the design of new benziodazolotetrazole materials with controlled performance or stability based on the modulation of the iodine bonds with its three ligands. The local mode analysis can serve as an effective tool to monitor the bond strengths, in particular to identify potential trigger bonds. We hope that this article will foster future collaboration between the experimental and computational community being engaged in vibrational spectroscopy. View Full-Text
Keywords: hypervalent iodine; vibrational spectroscopy; local vibrational mode theory; density functional theory; benziodazolotetrazoles; benziodoxoles; high-energy materials; explosives hypervalent iodine; vibrational spectroscopy; local vibrational mode theory; density functional theory; benziodazolotetrazoles; benziodoxoles; high-energy materials; explosives
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MDPI and ACS Style

Yannacone, S.; Sayala, K.D.; Freindorf, M.; Tsarevsky, N.V.; Kraka, E. Vibrational Analysis of Benziodoxoles and Benziodazolotetrazoles. Physchem 2021, 1, 45-68. https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010004

AMA Style

Yannacone S, Sayala KD, Freindorf M, Tsarevsky NV, Kraka E. Vibrational Analysis of Benziodoxoles and Benziodazolotetrazoles. Physchem. 2021; 1(1):45-68. https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010004

Chicago/Turabian Style

Yannacone, Seth, Kapil D. Sayala, Marek Freindorf, Nicolay V. Tsarevsky, and Elfi Kraka. 2021. "Vibrational Analysis of Benziodoxoles and Benziodazolotetrazoles" Physchem 1, no. 1: 45-68. https://0-doi-org.brum.beds.ac.uk/10.3390/physchem1010004

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