Crystal and Substituent Effects on Paramagnetic NMR Shifts in
Transition-Metal Complexes

J 2021

Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA et. al.

Základní údaje

Originální název

Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes

Autoři

NOVOTNÝ, Jan (203 Česká republika, domácí), Lukáš JEREMIAS (203 Česká republika, domácí), Patrick René NIMAX (276 Německo, domácí), Stanislav KOMOROVSKY (703 Slovensko), Ivo HEINMAA (233 Estonsko) a Radek MAREK (203 Česká republika, garant, domácí)

Vydání

Inorganic Chemistry, American Chemical Society, 2021, 0020-1669

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.inorgchem.1c00204

Impakt faktor

Impact factor: 5.436

Kód RIV

RIV/00216224:14740/21:00119015

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/acs.inorgchem.1c00204

UT WoS

000671099600019

Klíčová slova anglicky

NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction

Štítky

CF NMR, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 15. 10. 2024 14:16, Ing. Jana Kuchtová

Anotace

V originále

Nuclear magnetic resonance (NMR) spectroscopy of paramagnetic molecules provides detailed information about their molecular and electron-spin structure. The paramagnetic NMR spectrum is a very rich source of information about the hyperfine interaction between the atomic nuclei and the unpaired electron density. The Fermi-contact contribution to ligand hyperfine NMR shifts is particularly informative about the nature of the metal−ligand bonding and the structural arrangements of the ligands coordinated to the metal center. In this account, we provide a detailed experimental and theoretical NMR study of compounds of Cr(III) and Cu(II) coordinated with substituted acetylacetonate (acac) ligands in the solid state. For the first time, we report the experimental observation of extremely paramagnetically deshielded 13C NMR resonances for these compounds in the range of 900−1200 ppm. We demonstrate an excellent agreement between the experimental NMR shifts and those calculated using relativistic density-functional theory. Crystal packing is shown to significantly influence the NMR shifts in the solid state, as demonstrated by theoretical calculations of various supramolecular clusters. The resonances are assigned to individual atoms in octahedral Cr(acac)3 and square-planar Cu(acac)2 compounds and interpreted by different electron configurations and magnetizations at the central metal atoms resulting in different spin delocalizations and polarizations of the ligand atoms. Further, effects of substituents on the 13C NMR resonance of the ipso carbon atom reaching almost 700 ppm for Cr(acac)3 compounds are interpreted based on the analysis of Fermi-contact hyperfine contributions.

Návaznosti

GA18-05421S, projekt VaV

Název: Rozvoj paramagnetické NMR spektroskopie pro supramolekulární systémy (Akronym: SUPRAMAG)

Investor: Grantová agentura ČR, Rozvoj paramagnetické NMR spektroskopie pro supramolekulární systémy

GA21-06991S, projekt VaV

Název: Relativistické efekty v paramagnetické NMR spektroskopii (Akronym: RELMAG)

Investor: Grantová agentura ČR, Relativistické efekty v paramagnetické NMR spektroskopii

LM2018140, projekt VaV

Název: e-Infrastruktura CZ (Akronym: e-INFRA CZ)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, e-Infrastruktura CZ

90127, velká výzkumná infrastruktura

Název: CIISB II

Citovat

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA a Radek MAREK. Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes. Inorganic Chemistry. American Chemical Society, 2021, roč. 60, č. 13, s. 9368-9377. ISSN 0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.1c00204.

@article{1776582,
   author = {Novotný, Jan and Jeremias, Lukáš and Nimax, Patrick René and Komorovsky, Stanislav and Heinmaa, Ivo and Marek, Radek},
   article_number = {13},
   doi = {http://dx.doi.org/10.1021/acs.inorgchem.1c00204},
   keywords = {NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes},
   url = {https://doi.org/10.1021/acs.inorgchem.1c00204},
   volume = {60},
   year = {2021}
}

TY  - JOUR
ID  - 1776582
AU  - Novotný, Jan - Jeremias, Lukáš - Nimax, Patrick René - Komorovsky, Stanislav - Heinmaa, Ivo - Marek, Radek
PY  - 2021
TI  - Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes
JF  - Inorganic Chemistry
VL  - 60
IS  - 13
SP  - 9368-9377
EP  - 9368-9377
PB  - American Chemical Society
SN  - 00201669
KW  - NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction
UR  - https://doi.org/10.1021/acs.inorgchem.1c00204
N2  - Nuclear magnetic resonance (NMR) spectroscopy of paramagnetic molecules provides detailed information about their molecular and electron-spin structure. The paramagnetic NMR spectrum is a very rich source of information about the hyperfine interaction between the atomic nuclei and the unpaired electron density. The Fermi-contact contribution to ligand hyperfine NMR shifts is particularly informative about the nature of the metal−ligand bonding and the structural arrangements of the ligands coordinated to the metal center. In this account, we provide a detailed experimental and theoretical NMR study of compounds of Cr(III) and Cu(II) coordinated with substituted acetylacetonate (acac) ligands in the solid state. For the first time, we report the experimental observation of extremely paramagnetically deshielded 13C NMR resonances for these compounds in the range of 900−1200 ppm. We demonstrate an excellent agreement between the experimental NMR shifts and those calculated using relativistic density-functional theory. Crystal packing is shown to significantly influence the NMR shifts in the solid state, as demonstrated by theoretical calculations of various supramolecular clusters. The resonances are assigned to individual atoms in octahedral Cr(acac)3 and square-planar Cu(acac)2 compounds and interpreted by different electron configurations and magnetizations at the central metal atoms resulting in different spin delocalizations and polarizations of the ligand atoms. Further, effects of substituents on the 13C NMR resonance of the ipso carbon atom reaching almost 700 ppm for Cr(acac)3 compounds are interpreted based on the analysis of Fermi-contact hyperfine contributions.
ER  -

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA a Radek MAREK. Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes. \textit{Inorganic Chemistry}. American Chemical Society, 2021, roč.~60, č.~13, s.~9368-9377. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.1c00204.

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