Bonding and optical properties of spirocyclic-phosphazene derivatives. A DFT approach

Raúl Guajardo Maturana, María Luisa Valenzuela, Eduardo Schott, Macarena Rojas-Poblete

Resultado de la investigación: Article

8 Citas (Scopus)

Resumen

The bonding properties of phosphazenes and spirocyclophosphazenes containing tris-2,2′-dioxybiphenyl groups and their derivatives were investigated by means of different computational techniques. Electronic delocalization and phosphazene-ligand bonding were studied in terms of natural bond orbitals (NBOs) and energy decomposition (EDA) analysis in combination with the natural orbital for chemical valence (NOCV), which showed the dependency of the charge transfer with the electron delocalization. TD-DFT calculations were employed to study the absorption profile of the studied molecules and to contrast the redshift and change in intensities of the λmax. An assessment of second-order stabilization energies, ΔE2, within the NBO analysis revealed clear differences between the cyclic-phosphazene arrays. The EDA-NOCV showed that the ligand-phosphazene charge transfer is stronger in phosphazene with amine substituents (4c), which is due to the donor character of the substituent over the phenyl ring. The NBO analysis confirmed either the inflow or outflow of charge due to the influence of the electron donor or electron withdrawing groups.

Idioma originalEnglish
Páginas (desde-hasta)31479-31486
Número de páginas8
PublicaciónPhysical Chemistry Chemical Physics
Volumen19
N.º46
DOI
EstadoPublished - 1 ene 2017
Publicado de forma externa

Huella dactilar

phosphazene
Discrete Fourier transforms
Optical properties
Derivatives
optical properties
orbitals
Electrons
Charge transfer
Ligands
Amines
charge transfer
valence
Stabilization
ligands
electrons
Decomposition
Molecules
amines
stabilization
decomposition

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

Guajardo Maturana, R., Valenzuela, M. L., Schott, E., & Rojas-Poblete, M. (2017). Bonding and optical properties of spirocyclic-phosphazene derivatives. A DFT approach. Physical Chemistry Chemical Physics, 19(46), 31479-31486. https://doi.org/10.1039/c7cp06064e
Guajardo Maturana, Raúl ; Valenzuela, María Luisa ; Schott, Eduardo ; Rojas-Poblete, Macarena. / Bonding and optical properties of spirocyclic-phosphazene derivatives. A DFT approach. En: Physical Chemistry Chemical Physics. 2017 ; Vol. 19, N.º 46. pp. 31479-31486.
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Guajardo Maturana, R, Valenzuela, ML, Schott, E & Rojas-Poblete, M 2017, 'Bonding and optical properties of spirocyclic-phosphazene derivatives. A DFT approach', Physical Chemistry Chemical Physics, vol. 19, n.º 46, pp. 31479-31486. https://doi.org/10.1039/c7cp06064e

Bonding and optical properties of spirocyclic-phosphazene derivatives. A DFT approach. / Guajardo Maturana, Raúl; Valenzuela, María Luisa; Schott, Eduardo; Rojas-Poblete, Macarena.

En: Physical Chemistry Chemical Physics, Vol. 19, N.º 46, 01.01.2017, p. 31479-31486.

Resultado de la investigación: Article

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N2 - The bonding properties of phosphazenes and spirocyclophosphazenes containing tris-2,2′-dioxybiphenyl groups and their derivatives were investigated by means of different computational techniques. Electronic delocalization and phosphazene-ligand bonding were studied in terms of natural bond orbitals (NBOs) and energy decomposition (EDA) analysis in combination with the natural orbital for chemical valence (NOCV), which showed the dependency of the charge transfer with the electron delocalization. TD-DFT calculations were employed to study the absorption profile of the studied molecules and to contrast the redshift and change in intensities of the λmax. An assessment of second-order stabilization energies, ΔE2, within the NBO analysis revealed clear differences between the cyclic-phosphazene arrays. The EDA-NOCV showed that the ligand-phosphazene charge transfer is stronger in phosphazene with amine substituents (4c), which is due to the donor character of the substituent over the phenyl ring. The NBO analysis confirmed either the inflow or outflow of charge due to the influence of the electron donor or electron withdrawing groups.

AB - The bonding properties of phosphazenes and spirocyclophosphazenes containing tris-2,2′-dioxybiphenyl groups and their derivatives were investigated by means of different computational techniques. Electronic delocalization and phosphazene-ligand bonding were studied in terms of natural bond orbitals (NBOs) and energy decomposition (EDA) analysis in combination with the natural orbital for chemical valence (NOCV), which showed the dependency of the charge transfer with the electron delocalization. TD-DFT calculations were employed to study the absorption profile of the studied molecules and to contrast the redshift and change in intensities of the λmax. An assessment of second-order stabilization energies, ΔE2, within the NBO analysis revealed clear differences between the cyclic-phosphazene arrays. The EDA-NOCV showed that the ligand-phosphazene charge transfer is stronger in phosphazene with amine substituents (4c), which is due to the donor character of the substituent over the phenyl ring. The NBO analysis confirmed either the inflow or outflow of charge due to the influence of the electron donor or electron withdrawing groups.

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