Magnetically induced current density using London atomic orbitals of dihydroindeno-[1,2-b]-fluorenes

Cristina A. Barboza, Radovan Bast, Ezequiel Barboza, Desmond MacLeod-Carey, Ramiro Arratia-Perez

Research output: Contribution to journalArticle

Abstract

We present a study of the magnetically induced current density, calculated using London atomic orbitals, for the cis and trans isomers of dihydroindeno-[1,2-b]-fluorene (IF) and a set of 12 substituted macrocycles (where R = H, NH2, O-tBu, CH3, Si(CH3)3, OH, OCH3, F, Cl, Br, CN and NO2). Qualitative and quantitative analyses were done at Hartree-Fock and density functional theory (DFT) levels. The DFT results are not very sensitive to the choice of the density functional (BLYP and B3LYP). We found a linear correlation between the integrated magnetic susceptibilities values (χtotal) and Hammett parameters (σp) of the substituent group bonded directly to the outer six-member rings of the macrocycle structure. Our results suggest that the aromaticity of IF is not extensively modified by the presence of acceptor and donor substituent groups. The effect is rather local, and only strong π donor ligands lead to an aromaticity decrease of the outer six-member rings of the macrocycle directly attached to the substituent. Therefore, this series of indenofluorene derivatives correspond to a set of alternant aromatic and antiaromatic ring moieties, rather than a completely delocalized system. The effect of IF derivatives on the local aromaticity could not be reproduced using the nucleus independent chemical shift (NICS) calculations, which seem insensitive to the change of ligands.

Original languageEnglish
Pages (from-to)15648-15654
Number of pages7
JournalNew Journal of Chemistry
Volume42
Issue number19
DOIs
Publication statusPublished - 1 Jan 2018

Fingerprint

Fluorenes
Induced currents
Density functional theory
Current density
Ligands
Derivatives
Chemical shift
Magnetic susceptibility
Isomers

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

Barboza, Cristina A. ; Bast, Radovan ; Barboza, Ezequiel ; MacLeod-Carey, Desmond ; Arratia-Perez, Ramiro. / Magnetically induced current density using London atomic orbitals of dihydroindeno-[1,2-b]-fluorenes. In: New Journal of Chemistry. 2018 ; Vol. 42, No. 19. pp. 15648-15654.
@article{1a337e27db984be381fa26557b235896,
title = "Magnetically induced current density using London atomic orbitals of dihydroindeno-[1,2-b]-fluorenes",
abstract = "We present a study of the magnetically induced current density, calculated using London atomic orbitals, for the cis and trans isomers of dihydroindeno-[1,2-b]-fluorene (IF) and a set of 12 substituted macrocycles (where R = H, NH2, O-tBu, CH3, Si(CH3)3, OH, OCH3, F, Cl, Br, CN and NO2). Qualitative and quantitative analyses were done at Hartree-Fock and density functional theory (DFT) levels. The DFT results are not very sensitive to the choice of the density functional (BLYP and B3LYP). We found a linear correlation between the integrated magnetic susceptibilities values (χtotal) and Hammett parameters (σp) of the substituent group bonded directly to the outer six-member rings of the macrocycle structure. Our results suggest that the aromaticity of IF is not extensively modified by the presence of acceptor and donor substituent groups. The effect is rather local, and only strong π donor ligands lead to an aromaticity decrease of the outer six-member rings of the macrocycle directly attached to the substituent. Therefore, this series of indenofluorene derivatives correspond to a set of alternant aromatic and antiaromatic ring moieties, rather than a completely delocalized system. The effect of IF derivatives on the local aromaticity could not be reproduced using the nucleus independent chemical shift (NICS) calculations, which seem insensitive to the change of ligands.",
author = "Barboza, {Cristina A.} and Radovan Bast and Ezequiel Barboza and Desmond MacLeod-Carey and Ramiro Arratia-Perez",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/C8NJ02301H",
language = "English",
volume = "42",
pages = "15648--15654",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "19",

}

Magnetically induced current density using London atomic orbitals of dihydroindeno-[1,2-b]-fluorenes. / Barboza, Cristina A.; Bast, Radovan; Barboza, Ezequiel; MacLeod-Carey, Desmond; Arratia-Perez, Ramiro.

In: New Journal of Chemistry, Vol. 42, No. 19, 01.01.2018, p. 15648-15654.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Magnetically induced current density using London atomic orbitals of dihydroindeno-[1,2-b]-fluorenes

AU - Barboza, Cristina A.

AU - Bast, Radovan

AU - Barboza, Ezequiel

AU - MacLeod-Carey, Desmond

AU - Arratia-Perez, Ramiro

PY - 2018/1/1

Y1 - 2018/1/1

N2 - We present a study of the magnetically induced current density, calculated using London atomic orbitals, for the cis and trans isomers of dihydroindeno-[1,2-b]-fluorene (IF) and a set of 12 substituted macrocycles (where R = H, NH2, O-tBu, CH3, Si(CH3)3, OH, OCH3, F, Cl, Br, CN and NO2). Qualitative and quantitative analyses were done at Hartree-Fock and density functional theory (DFT) levels. The DFT results are not very sensitive to the choice of the density functional (BLYP and B3LYP). We found a linear correlation between the integrated magnetic susceptibilities values (χtotal) and Hammett parameters (σp) of the substituent group bonded directly to the outer six-member rings of the macrocycle structure. Our results suggest that the aromaticity of IF is not extensively modified by the presence of acceptor and donor substituent groups. The effect is rather local, and only strong π donor ligands lead to an aromaticity decrease of the outer six-member rings of the macrocycle directly attached to the substituent. Therefore, this series of indenofluorene derivatives correspond to a set of alternant aromatic and antiaromatic ring moieties, rather than a completely delocalized system. The effect of IF derivatives on the local aromaticity could not be reproduced using the nucleus independent chemical shift (NICS) calculations, which seem insensitive to the change of ligands.

AB - We present a study of the magnetically induced current density, calculated using London atomic orbitals, for the cis and trans isomers of dihydroindeno-[1,2-b]-fluorene (IF) and a set of 12 substituted macrocycles (where R = H, NH2, O-tBu, CH3, Si(CH3)3, OH, OCH3, F, Cl, Br, CN and NO2). Qualitative and quantitative analyses were done at Hartree-Fock and density functional theory (DFT) levels. The DFT results are not very sensitive to the choice of the density functional (BLYP and B3LYP). We found a linear correlation between the integrated magnetic susceptibilities values (χtotal) and Hammett parameters (σp) of the substituent group bonded directly to the outer six-member rings of the macrocycle structure. Our results suggest that the aromaticity of IF is not extensively modified by the presence of acceptor and donor substituent groups. The effect is rather local, and only strong π donor ligands lead to an aromaticity decrease of the outer six-member rings of the macrocycle directly attached to the substituent. Therefore, this series of indenofluorene derivatives correspond to a set of alternant aromatic and antiaromatic ring moieties, rather than a completely delocalized system. The effect of IF derivatives on the local aromaticity could not be reproduced using the nucleus independent chemical shift (NICS) calculations, which seem insensitive to the change of ligands.

UR - http://www.scopus.com/inward/record.url?scp=85054016111&partnerID=8YFLogxK

U2 - 10.1039/C8NJ02301H

DO - 10.1039/C8NJ02301H

M3 - Article

VL - 42

SP - 15648

EP - 15654

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 19

ER -