Magnetization Dynamics and Coherent Spin Manipulation of a Propeller Gd(III) Complex with the Smallest Helicene Ligand

Gabriela Handzlik; Michał Magott; Mirosław Arczyński; Alena M Sheveleva; Floriana Tuna; Marcin Sarewicz; Artur Osyczka; Michał Rams; Veacheslav Vieru; Liviu F Chibotaru; Dawid Pinkowicz

doi:10.1021/acs.jpclett.9b03275

Magnetization Dynamics and Coherent Spin Manipulation of a Propeller Gd(III) Complex with the Smallest Helicene Ligand

J Phys Chem Lett. 2020 Feb 20;11(4):1508-1515. doi: 10.1021/acs.jpclett.9b03275. Epub 2020 Feb 7.

Affiliations

¹ Faculty of Chemistry , Jagiellonian University , Gronostajowa 2 , 30-387 Kraków , Poland.
² School of Chemistry and Photon Science Institute , The University of Manchester , Oxford Road , Manchester M13 9PL , United Kingdom.
³ Department of Molecular Biophysics, Faculty of Biochemistry, Biophysics and Biotechnology , Jagiellonian University , Gronostajowa 7 , 30-387 Kraków , Poland.
⁴ Marian Smoluchowski Institute of Physics , Jagiellonian University , Łojasiewicza 11 , 30-348 Kraków , Poland.
⁵ Theory and Nanomaterials Group , Katholieke Universiteit Leuven , Celestijnenlaan 200F , 3001 Leuven , Belgium.

Abstract

A homoleptic gadolinium(III) complex with the smallest helicene-type ligand, 1,10-phenanthroline-N,N'-dioxide (phendo) [Gd(phendo)₄](NO₃)₃·xMeOH (phendo = 1,10-phenanthroline-N,N'-dioxide, MeOH = methanol), shows slow relaxation of the magnetization characteristic for Single Ion Magnets (SIM), despite negligible magnetic anisotropy, confirmed by ab initio calculations. Solid state dilution magnetic and EPR studies reveal that the magnetization dynamics of the [Gd(phendo)₄]³⁺ cation is controlled mainly by a Raman process. Pulsed EPR experiments demonstrate long phase memory times (up to 2.7 μs at 5 K), enabling the detection of Rabi oscillations at 20 K, which confirms coherent control of its spin state.