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Theoretical study of the effects of substituents (F, Cl, Br, CH3, and CN) on the aromaticity of borazine

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Abstract

This paper presents a theoretical study of the effects of substituents (F, Cl, Br, CH3, and CN) on the aromaticity of borazine (B3N3H6), using density functional theory (DFT) and the Hartree-Fock (HF) method. The calculations to optimize the geometries, structural properties, and vibrational frequencies were performed using the same 6–311G(d,p) and 6–311++G(d,p) basis sets, comparing the methods with experimental results. In the analysis of the NICSZZ values, it was found that that replacing the hydrogen atoms by halogen atoms (F, Cl, and Br) and CH3 reduced the aromaticity of the borazine molecule, while use of the CN group resulted in NICSZZ values (0.9–2.0 Å) very close to those of borazine, presenting the following order of increasing aromaticity: B3N3H3-(Br)3 < B3N3H3-(Cl)3 < B3N3H3-(F)3 < B3N3H3-(CH3)3 < B3N3H6 ~ B3N3H3-(CN)3. All the spectra of the compounds showed only the presence of transition peaks distant from the UV region, reflecting the large energy difference between the HOMO and LUMO orbitals. After the substitution of the borazine ring, all the compounds presented an intensification of the spectrum, with a shift of the maximum absorbance toward red, indicative of a bathochromic effect. There was a direct inverse relation between the energy gap and the maximum wavelength of the compounds.

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Acknowledgments

The authors are grateful for the financial support provided by CAPES, FINEP, CNPq, and FAPEMA.

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Authors and Affiliations

  1. Universidade Federal de São Carlos, São Carlos, SP, CEP 13565-905, Brazil

    Alexandre Costa & Elizama Ramos Costa

  2. Universidade Estadual do Maranhão, CP 09, São Luís, MA, 65080-040, Brazil

    Adilson Luís Pereira Silva

  3. Universidade Federal do Maranhão, São Luís, MA, 65080-805, Brazil

    Auro Atsushi Tanaka & Jaldyr de Jesus Gomes Jr

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Correspondence to Jaldyr de Jesus Gomes Jr.

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Costa, A., Costa, E.R., Silva, A.L.P. et al. Theoretical study of the effects of substituents (F, Cl, Br, CH3, and CN) on the aromaticity of borazine. J Mol Model 24, 34 (2018). https://doi.org/10.1007/s00894-017-3555-x

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