Spatial Contributions to H-1 NMR Chemical Shifts of Free-Base Porphyrinoids

Heike Fliegl; Maria Dimitrova; Raphael J. F. Berger; Dage Sundholm

doi:10.3390/chemistry3030072

Spatial Contributions to H-1 NMR Chemical Shifts of Free-Base Porphyrinoids

Heike Fliegl, Maria Dimitrova, Raphael J. F. Berger, Dage Sundholm

Chemistry and Physics of Materials

Research output: Contribution to journal › Article › peer-review

Abstract

A recently developed methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities is used for studying spatial contributions including ring-current contributions to 1H nuclear magnetic resonance (NMR) chemical shifts of aromatic and anti-aromatic free-base porphyrinoids. Our approach allows a visual inspection of the spatial origin of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constants. Diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions implying that not merely the tropicity of the current density determines whether the contribution has a shielding or deshielding character. Instead the shielding or deshielding contribution is determined by the direction of the current-density flux with respect to the studied nucleus.

Original language	English
Pages (from-to)	1005-1021
Number of pages	17
Journal	Chemistry
Volume	3
DOIs	https://doi.org/10.3390/chemistry3030072
Publication status	Published - 5 Sept 2021

Keywords

Theretical Chemistry
London orbitals
gauge-including atomic orbitals
magnetically induced current densities
nuclear magnetic shielding constants

Fields of Science and Technology Classification 2012

104 Chemistry

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10.3390/chemistry3030072

Cite this

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title = "Spatial Contributions to H-1 NMR Chemical Shifts of Free-Base Porphyrinoids",

abstract = "A recently developed methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities is used for studying spatial contributions including ring-current contributions to 1H nuclear magnetic resonance (NMR) chemical shifts of aromatic and anti-aromatic free-base porphyrinoids. Our approach allows a visual inspection of the spatial origin of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constants. Diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions implying that not merely the tropicity of the current density determines whether the contribution has a shielding or deshielding character. Instead the shielding or deshielding contribution is determined by the direction of the current-density flux with respect to the studied nucleus.",

keywords = "Theretical Chemistry, London orbitals, gauge-including atomic orbitals, magnetically induced current densities, nuclear magnetic shielding constants",

author = "Heike Fliegl and Maria Dimitrova and Berger, {Raphael J. F.} and Dage Sundholm",

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doi = "10.3390/chemistry3030072",

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AU - Fliegl, Heike

AU - Dimitrova, Maria

AU - Berger, Raphael J. F.

AU - Sundholm, Dage

PY - 2021/9/5

Y1 - 2021/9/5

N2 - A recently developed methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities is used for studying spatial contributions including ring-current contributions to 1H nuclear magnetic resonance (NMR) chemical shifts of aromatic and anti-aromatic free-base porphyrinoids. Our approach allows a visual inspection of the spatial origin of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constants. Diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions implying that not merely the tropicity of the current density determines whether the contribution has a shielding or deshielding character. Instead the shielding or deshielding contribution is determined by the direction of the current-density flux with respect to the studied nucleus.

AB - A recently developed methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities is used for studying spatial contributions including ring-current contributions to 1H nuclear magnetic resonance (NMR) chemical shifts of aromatic and anti-aromatic free-base porphyrinoids. Our approach allows a visual inspection of the spatial origin of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constants. Diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions implying that not merely the tropicity of the current density determines whether the contribution has a shielding or deshielding character. Instead the shielding or deshielding contribution is determined by the direction of the current-density flux with respect to the studied nucleus.

KW - Theretical Chemistry

KW - London orbitals

KW - gauge-including atomic orbitals

KW - magnetically induced current densities

KW - nuclear magnetic shielding constants

UR - https://doi.org/10.3390/chemistry3030072

UR - https://www.mendeley.com/catalogue/90f6497d-6b1e-313b-8de1-7a92697b587f/

U2 - 10.3390/chemistry3030072

DO - 10.3390/chemistry3030072

M3 - Article

SN - 0861-9255

VL - 3

SP - 1005

EP - 1021

JO - Chemistry

JF - Chemistry

ER -

Spatial Contributions to H-1 NMR Chemical Shifts of Free-Base Porphyrinoids

Abstract

Keywords

Fields of Science and Technology Classification 2012

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