Role of donor-acceptor functional groups in N3P3 cyclic-triphosphazene backbone. Unraveling bonding characteristics from natural orbitals within an extended transition state-natural orbital for the chemical valence scheme

Cristian Linares-Flores, Rodrigo Ramirez-Tagle, Macarena Rojas-Poblete, Ramiro Arratia-Perez, Alvaro Muñoz-Castro, Raul Guajardo-Maturana

Research output: Contribution to journalArticle

Abstract

The formation of cyclophosphazenes containing several ligands or substituent groups gives rise to an attractive derivative set, for development of novel applications, with variable properties. Here, it is possible to unravel the role of different functional groups attached to the N 3P 3 backbone, to reach a better understanding of the bonding character in the cyclic [─P─N─] skeleton. We employed the extended transition state-natural orbital for the chemical valence scheme to unravel the σ and π orbital kernels that are involved in the assembling of such structures, by varying the acceptor-donor characteristics of the ─CF 3, ─NO 2, ─COOH, ─CN, ─NH 2, ─OH, and ─OCH 3 groups, where ─NO 2 behaves as a stronger electron-withdrawing substituent rather than ─CF 3, ─COOH, and ─CN, denoting that the nature of the ligand-phosphazene interaction contributes to some degree to the bond strength of the cyclic [─P─N─] backbone. Our results reveal that the electron-withdrawing ─NO 2 group leads to higher σ and π [─P─N─] orbital-energy contributions, which is reflected in a shortening of the [─P─N─] distance, contrasting with the case of electron-donating groups such as ─NH 2, ─OH, and ─OCH 3 within the phosphazene set. These insights allow further variation and modulation of the bonding in the [─P─N─] ring.

Original languageEnglish
Article numbere26057
JournalInternational Journal of Quantum Chemistry
Volume120
Issue number1
DOIs
Publication statusPublished - 1 Jan 2020

Keywords

  • cyclic-phosphazene
  • ETS-NOCV
  • sigma and pi contributions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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