Impact of Counter Ion Methyl Groups on Spin Relaxation in [V(C6H4O2)3]2-

Cassidy E. Jackson, Thacien Ngendahimana, Chun Yi Lin, Gareth R. Eaton, Sandra S. Eaton, Joseph M. Zadrozny

研究成果: Article同行評審

3 引文 斯高帕斯(Scopus)


A detailed understanding of how counterion methyl groups affect electron spin relaxation is key to using these chemical species in the design of new molecular qubits. Here, we study the coherent spin dynamics of the V(IV) complex [V(C6H4O2)3]2-with five different countercations: (Et3NH)+(1), (n-Bu3NH)+(2), (n-Bu3N-2H)+(2-d2), (n-Hex3NH)+(3), and (n-Oct3NH)+(4). These counterions systematically increase the distance between the V(IV) spin and the methyl group of the alkyl chains. Pulsed electron paramagnetic resonance investigations in both glassy solutions and solid-state dilutions show that (1) the counterions are bound via hydrogen bonding to the [V(C6H4O2)3]2-unit, even in frozen solutions, and that (2) the methyl group of the counterion has a dominant role in dictating the spin-spin (or phase memory) relaxation. We can reproduce the rate of the spin echo decay with a model that is based on the distance-dependent impact of the counterion methyl groups, and we note that in 1, the methyl groups generate a modulation of the echo decay. We also show that an important instrumental setting of the spin echo measurement, the shot repetition time, can have a dramatic impact on the shape of the echo decay curve and thus the measured relaxation times. Finally, the spin-lattice relaxation times are independent of cation and are the same, within experimental uncertainty, in glassy o-terphenyl and in the V(IV) complexes doped into the closed-shell Ti(IV) analogue, (n-Bu3NH)2[Ti(C6H4O2)3] (2-Ti). Together, these data provide a mechanistic picture of how counterion CH3groups modulate phase memory spin relaxation in open-shell metal complexes.

頁(從 - 到)7169-7176
期刊Journal of Physical Chemistry C
出版狀態Published - 2022 4月 28

All Science Journal Classification (ASJC) codes

  • 電子、光磁材料
  • 一般能源
  • 物理與理論化學
  • 表面、塗料和薄膜


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