Tetragallium(III) complex in [Ga4(L4-Py)2(dpm)6]•EtOH, with H3L4-Py = 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol and Hdpm = dipivaloylmethane, was investigated as a diamagnetic analogue of tetrametallic, propeller-like single-molecule magnets (SMMs). The chiral molecular structure partitions the six CH2 protons of each (L4-Py)3- tripodal ligand into two diastereotopic sets. The two signals were clearly detected by 1H NMR spectroscopy in C6D6, proving that Λ and Δ enantiomers interconvert slowly over NMR timescale. Density functional theory calculations provided quantitative agreement with the observed values of chemical shifts and scalar coupling constants across both geminal and long-range interaction pathways. The solid-state structure suggests the occurrence of a lower symmetry stereoisomer (27 mol%), which was clearly identified in the NMR spectra. Since Fe3+ forms distinctly more inert complexes than Ga3+, comparable or greater configurational stability is expected for the isostructural FeIII4, FeIII3CrIII, and FeIII3VIII SMMs, which are difficult to investigate by solution NMR because of the strong paramagnetism.

Stereoisomerism in Tetrametallic Propeller-like Complexes: a Solid-state and Solution NMR Study on a Tetragallium(III) Derivative / Cornia, Andrea; Mucci, Adele; Briganti, Matteo; Bridonneau, Nathalie; Nava, Andrea; Nicolini, Alessio. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1099-0682. - 2022:1(2022), pp. 0-0. [10.1002/ejic.202100873]

Stereoisomerism in Tetrametallic Propeller-like Complexes: a Solid-state and Solution NMR Study on a Tetragallium(III) Derivative

Andrea Cornia
;
Adele Mucci;Nathalie Bridonneau;Andrea Nava;Alessio Nicolini
2022

Abstract

Tetragallium(III) complex in [Ga4(L4-Py)2(dpm)6]•EtOH, with H3L4-Py = 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol and Hdpm = dipivaloylmethane, was investigated as a diamagnetic analogue of tetrametallic, propeller-like single-molecule magnets (SMMs). The chiral molecular structure partitions the six CH2 protons of each (L4-Py)3- tripodal ligand into two diastereotopic sets. The two signals were clearly detected by 1H NMR spectroscopy in C6D6, proving that Λ and Δ enantiomers interconvert slowly over NMR timescale. Density functional theory calculations provided quantitative agreement with the observed values of chemical shifts and scalar coupling constants across both geminal and long-range interaction pathways. The solid-state structure suggests the occurrence of a lower symmetry stereoisomer (27 mol%), which was clearly identified in the NMR spectra. Since Fe3+ forms distinctly more inert complexes than Ga3+, comparable or greater configurational stability is expected for the isostructural FeIII4, FeIII3CrIII, and FeIII3VIII SMMs, which are difficult to investigate by solution NMR because of the strong paramagnetism.
2022
9-nov-2021
2022
1
0
0
Stereoisomerism in Tetrametallic Propeller-like Complexes: a Solid-state and Solution NMR Study on a Tetragallium(III) Derivative / Cornia, Andrea; Mucci, Adele; Briganti, Matteo; Bridonneau, Nathalie; Nava, Andrea; Nicolini, Alessio. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1099-0682. - 2022:1(2022), pp. 0-0. [10.1002/ejic.202100873]
Cornia, Andrea; Mucci, Adele; Briganti, Matteo; Bridonneau, Nathalie; Nava, Andrea; Nicolini, Alessio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1255297
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