Counterion influence on dynamic spin properties in a V(iv) complex

Chun-Yi Lin, Thacien Ngendahimana, Gareth R. Eaton, Sandra S. Eaton, Joseph M. Zadrozny

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Using transition metal ions for spin-based applications, such as electron paramagnetic resonance imaging (EPRI) or quantum computation, requires a clear understanding of how local chemistry influences spin properties. Herein we report a series of four ionic complexes to provide the first systematic study of one aspect of local chemistry on the V(iv) spin-the counterion. To do so, the four complexes (Et 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (1), (n-Bu 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (2), (n-Hex 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (3), and (n-Oct 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (4) were probed by EPR spectroscopy in solid state and solution. Room temperature, solution X-band (ca. 9.8 GHz) continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy revealed an increasing linewidth with larger cations, likely a counterion-controlled tumbling in solution via ion pairing. In the solid state, variable-temperature (5-180 K) X-band (ca. 9.4 GHz) pulsed EPR studies of 1-4 in o-terphenyl glass demonstrated no effect on spin-lattice relaxation times (T 1 ), indicating little role for the counterion on this parameter. However, the phase memory time (T m ) of 1 below 100 K is markedly smaller than those of 2-4. This result is counterintuitive, as 2-4 are relatively richer in 1 H nuclear spin, hence, expected to have shorter T m . Thus, these data suggest an important role for counterion methyl groups on T m , and moreover provide the first instance of a lengthening T m with increasing nuclear spin quantity on a molecule.

Original languageEnglish
Pages (from-to)548-555
Number of pages8
JournalChemical Science
Volume10
Issue number2
DOIs
Publication statusPublished - 2019 Jan 1

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Spin dynamics
Paramagnetic resonance
Spectroscopy
Barreling
Quantum computers
Spin-lattice relaxation
Linewidth
Relaxation time
Transition metals
Metal ions
Cations
Ions
Imaging techniques
Data storage equipment
Glass
Temperature
Molecules

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Lin, C-Y., Ngendahimana, T., Eaton, G. R., Eaton, S. S., & Zadrozny, J. M. (2019). Counterion influence on dynamic spin properties in a V(iv) complex. Chemical Science, 10(2), 548-555. https://doi.org/10.1039/c8sc04122a
Lin, Chun-Yi ; Ngendahimana, Thacien ; Eaton, Gareth R. ; Eaton, Sandra S. ; Zadrozny, Joseph M. / Counterion influence on dynamic spin properties in a V(iv) complex. In: Chemical Science. 2019 ; Vol. 10, No. 2. pp. 548-555.
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Lin, C-Y, Ngendahimana, T, Eaton, GR, Eaton, SS & Zadrozny, JM 2019, 'Counterion influence on dynamic spin properties in a V(iv) complex', Chemical Science, vol. 10, no. 2, pp. 548-555. https://doi.org/10.1039/c8sc04122a

Counterion influence on dynamic spin properties in a V(iv) complex. / Lin, Chun-Yi; Ngendahimana, Thacien; Eaton, Gareth R.; Eaton, Sandra S.; Zadrozny, Joseph M.

In: Chemical Science, Vol. 10, No. 2, 01.01.2019, p. 548-555.

Research output: Contribution to journalArticle

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AU - Lin, Chun-Yi

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AB - Using transition metal ions for spin-based applications, such as electron paramagnetic resonance imaging (EPRI) or quantum computation, requires a clear understanding of how local chemistry influences spin properties. Herein we report a series of four ionic complexes to provide the first systematic study of one aspect of local chemistry on the V(iv) spin-the counterion. To do so, the four complexes (Et 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (1), (n-Bu 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (2), (n-Hex 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (3), and (n-Oct 3 NH) 2 [V(C 6 H 4 O 2 ) 3 ] (4) were probed by EPR spectroscopy in solid state and solution. Room temperature, solution X-band (ca. 9.8 GHz) continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy revealed an increasing linewidth with larger cations, likely a counterion-controlled tumbling in solution via ion pairing. In the solid state, variable-temperature (5-180 K) X-band (ca. 9.4 GHz) pulsed EPR studies of 1-4 in o-terphenyl glass demonstrated no effect on spin-lattice relaxation times (T 1 ), indicating little role for the counterion on this parameter. However, the phase memory time (T m ) of 1 below 100 K is markedly smaller than those of 2-4. This result is counterintuitive, as 2-4 are relatively richer in 1 H nuclear spin, hence, expected to have shorter T m . Thus, these data suggest an important role for counterion methyl groups on T m , and moreover provide the first instance of a lengthening T m with increasing nuclear spin quantity on a molecule.

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