Reactions of hexakis(acetonitrile)iron(II) hexafluorophosphate in acetonitrile. Ligation of ammonia, pyridine, and trimethylamine to iron(II) and the behaviour of trimethyl phosphite and trimethylphosphine towards iron(II), nitrogen donor ligand complex cations

McGhee, Laurence; Siddique, Rana M.; Winfield, John M.

doi:10.1039/dt9880001309

Cited by 14 publications

(8 citation statements)

References 2 publications

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“…15 We thus targeted Fe(MeCN) 6 (BF 4 ) 2 as the precursor for introducing Fe II into the P4VP-SWCNT network, with the expectation that the labile acetonitrile ligand will allow fast irreversible ligand exchange with the stronger pyridyl ligands or P4VP. 16 Following the outlined strategy, we treated the surfaceanchored P4VP-SWCNT composite with Fe(MeCN) 6 (BF 4 ) 2 for 4 h under nitrogen atmosphere before rinsing with solvents to remove the unbound Fe species (Figure S1). Scanning electron microscopy imaging of the Fe-composite on glass confirmed the presence of a robust nanotube network after multistep manipulations (Figure S2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Wireless Oxygen Sensors Enabled by Fe(II)-Polymer Wrapped Carbon Nanotubes

et al. 2017

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Oxygen causes food spoilage and drug degradation, which is addressed commercially by modified atmosphere packaging. We report herein a wireless oxygen sensor, O-p-CARD, from solution processed Fe-poly(4-vinylpyridine)-single-walled carbon nanotube composites on commercial passive near-field communication tags. A large irreversible attenuation in the reflection signal of an O-p-CARD was observed in response to oxygen at relevant concentrations, enabling non-line-of-sight monitoring of modified atmosphere packaging. These devices allow for cumulative oxygen exposure inside a package to be read with a conventional smartphone. We have demonstrated that an O-p-CARD can detect air ingress into a nitrogen-filled vegetable package at ambient conditions. This technology provides an inexpensive, heavy-metal-free, and smartphone-readable method for in situ non-line-of-sight quality monitoring of oxygen-sensitive packaged products.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…In fact, iron compounds are widely used as oxygen scavengers for packaging . We thus targeted Fe(MeCN) 6 (BF 4 ) 2 as the precursor for introducing Fe II into the P4VP-SWCNT network, with the expectation that the labile acetonitrile ligand will allow fast irreversible ligand exchange with the stronger pyridyl ligands or P4VP …”

Section: Resultsmentioning

confidence: 99%

Wireless Oxygen Sensors Enabled by Fe(II)-Polymer Wrapped Carbon Nanotubes

et al. 2017

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“…The cations are ideal starting points for investigation of the coordination chemistry of the elements involved and we have recently reported the behaviour of simple N-and P-donor ligands towards iron(I1) in this solvent (2). An extension of this work to a study of reactions occurring between dimethyl sulphide, trimethylamine, or trimethylphosphine and solvated copper(I1) or thallium(II1) cations is now reported.…”

Section: Introductionmentioning

confidence: 96%

The oxidation of dimethyl sulphide, trimethylamine, and trimethylphosphine by solvated copper(II) or thallium(III) hexafluorometallates in acetonitrile

Siddique¹,

Winfield²

1989

Can. J. Chem.

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“…Experimentally, bands at 12 400 and 9000 cm -1 have been assigned to components of the 5 T2g → 5 Eg(2a,2b) transition. 54 Here, for the X-ray idealized structure, the 5 Eg(2a,2b) and 5 Eg(1a,1b) states are calculated at 11 250/11 255 cm -1 and 145/240 cm -1 , respectively, while the lowest energy triplet and singlet states are 11 380 cm -1 and 11 640 cm -1 , respectively. The relatively large ZFS for the X-ray idealized structure of [Fe(NH3)6] 2+ is consistent with a the low energies of the 5 Eg(1a,1b) states, which contribute ~31.6 cm -1 to the total axial ZFS, with a small ~1.6 cm -1 contribution from the lowest energy triplet.…”

Section: -mentioning

confidence: 99%

Spin–phonon coupling and dynamic zero-field splitting contributions to spin conversion processes in iron(II) complexes

Higdon

Barth

Kozlowski

et al. 2020

The Journal of Chemical Physics

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Magnetization dynamics of transition metal complexes manifest in properties and phenomena of fundamental and applied interest (e.g., slow magnetic relaxation in single molecule magnets (SMMs), quantum coherence in quantum bits (qubits), and intersystem crossing (ISC) rates in photophysics). While spin-phonon coupling is recognized as an important determinant of these dynamics, additional fundamental studies are required to unravel the nature of the coupling and thus leverage it in molecular engineering approaches. To this end, we describe here a combined ligand field theory and multireference ab initio model to define spin-phonon coupling terms in S = 2 transition metal complexes and demonstrate how couplings originate from both the static and dynamic properties of ground and excited states. By extending concepts to spin conversion processes, ligand field dynamics manifest in the evolution of the excited state origins of zero-field splitting (ZFS) along specific normal mode potential energy surfaces. Dynamic ZFSs provide a powerful means to independently evaluate contributions from spin-allowed and/or-forbidden excited states to spin-phonon coupling terms. Furthermore, ratios between various intramolecular coupling terms for a given mode drive spin conversion processes in transition metal complexes and can be used to analyze mechanisms of ISC. Variations in geometric structure strongly influence the relative intramolecular linear spin-phonon coupling terms and will thus define the overall spin state dynamics. While of general importance for understanding magnetization dynamics, this study links the phenomenon of spin-phonon coupling across fields of single molecule magnetism, quantum materials/qubits, and transition metal photophysics. File list (2) download file view on ChemRxiv Fe_SPC_MS_rxiv.pdf (4.18 MiB) download file view on ChemRxiv Fe_SPC_SI_rxiv.pdf (3.66 MiB)

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Reactions of hexakis(acetonitrile)iron(II) hexafluorophosphate in acetonitrile. Ligation of ammonia, pyridine, and trimethylamine to iron(II) and the behaviour of trimethyl phosphite and trimethylphosphine towards iron(II), nitrogen donor ligand complex cations

Cited by 14 publications

References 2 publications

Wireless Oxygen Sensors Enabled by Fe(II)-Polymer Wrapped Carbon Nanotubes

Wireless Oxygen Sensors Enabled by Fe(II)-Polymer Wrapped Carbon Nanotubes

The oxidation of dimethyl sulphide, trimethylamine, and trimethylphosphine by solvated copper(II) or thallium(III) hexafluorometallates in acetonitrile

Spin–phonon coupling and dynamic zero-field splitting contributions to spin conversion processes in iron(II) complexes

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