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Intermolecular perturbation in the self-assembly of melamine

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Abstract

A theoretical study has been conducted on a set of supramolecular complexes based on 1,3,5-triazine-2,4,6-triamine, or melamine (M), with cyanuric acid (CA), trithiocyanuric acid (TCA), and two mono-substituted derivatives of CA with chlorine (CACl) and bromine (CABr). The study was carried out on 12 complexes, M/(CA) n , M/(TCA) n , M/(CACl) n , M/(CABr) n , with n = 1, 2 and 3, by the density functional theory employing the ω-B97XD functional with the 6-311++G(d,p) basis set. Information about the intermolecular perturbation over M and the interactions that drive the self-assembly of these species has been obtained from the quantum theory of atoms in molecules and a natural bond orbital analysis. The harmonic oscillator model of aromaticity, the para-delocalization index, the fluctuation aromatic index, and two electron charge density descriptors were used to evaluate the aromaticity of M in each complex. Results show that the hydrogen and halogen (XBs) bond interactions, which direct the self-assembly process in these complexes, are anti-cooperative. Binding energies decrease in the following order: M/(CA) n  > M/(TCA) n  > M/(CABr) n  > M/(CACl) n (for all values of n). Brominated CA arises as a potential compound to self-assembly with M via XBs.

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Acknowledgments

We would like to thank SECYT UTN (Secretaría de Ciencia y Tecnología – Universidad Tecnológica Nacional), for financial support. A.N.P. is a fellowship researcher of CONICET, Argentina (Consejo Nacional de Investigaciones Científicas y Técnicas), and N.M.P. is a career researcher of CONICET, Argentina.

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Authors and Affiliations

  1. Grupo de Investigación en Química Teórica y Experiental (QuiTEx), Facultad Regional Resistencia, Universidad Tecnológica Nacional, French 414, 3500, Resistencia, Chaco, Argentina

    A. N. Petelski, S. C. Pamies & G. L. Sosa

  2. Laboratorio de Estructura Molecular y Propiedades (LEMYP), Área de Química Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, Universidad Nacional del Nordeste, Avenida Libertad 5460, 3400, Corrientes, Argentina

    Darío J. R. Duarte & N. M. Peruchena

  3. IQUIBA-NEA (UNNE-CONICET), Avenida Libertad 5460, 3400, Corrientes, Argentina

    A. N. Petelski, Darío J. R. Duarte, N. M. Peruchena & G. L. Sosa

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  1. A. N. Petelski
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  2. Darío J. R. Duarte
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  3. S. C. Pamies
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Correspondence to G. L. Sosa.

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Petelski, A.N., Duarte, D.J.R., Pamies, S.C. et al. Intermolecular perturbation in the self-assembly of melamine. Theor Chem Acc 135, 65 (2016). https://doi.org/10.1007/s00214-015-1795-3

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