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

Abstract

A homoleptic gadolinium(III) complex with the smallest helicene-type ligand, 1,10-phenanthroline- N , N ′-dioxide (phendo) [Gd(phendo) 4 ](NO 3 ) 3 · x MeOH (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.

Identical anomalous Raman relaxation exponent in a family of single ion magnets: towards reliable Raman relaxation determination?

“…Due to the presence of two relaxation processes for both undiluted compounds, the dynamic magnetic properties of the solid state diluted samples Er2% and Yb2% were also studied (the solid state dilution suppresses the dipole-dipole interactions between the Er III or Yb III centers enabling a straightforward analysis of the AC data). According to our previous study of the isostructural Gd III -based complex 39 the solid state dilution lower than 3% effectively switches off the dipole-dipole interactions. The exact concentrations of the Er III in Er2% and Yb III in Yb2% were determined by ICP-OES analysis (see Table S5 in the ESI for details).…”

“…4,32,33 Moreover, deep understanding of relaxation mechanisms for SIMs which do not possess pure mJ ground states is also important from the point of view of molecular qubit candidates design, demonstrated for several non-dysprosium complexes so far. [34][35][36][37][38][39][40] Herein we present a thorough magnetic and EPR study of three lanthanide-based SIMs from the family of [Ln(phendo)4](NO3)3•xMeOH (Ln = Gd (Gd), Er (Er), Yb (Yb), phendo = 1,10-phenanthroline-N,N'-dioxide). The complexes show four-bladed propeller-like geometry enforced by the helicene-type phendo ligands.…”

“…The complexes show four-bladed propeller-like geometry enforced by the helicene-type phendo ligands. Gd was described in our previous work 39 and is presented here as a benchmark where the relaxation of the magnetization is dominated by the Raman process. The family is expanded by the addition of two analogues based on Er III and Yb III : Er and Yb.…”

Molecular and Polymer Ln2M2 (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

“…Magnetic measurements showed that gadolinium (II and VII) and dysprosium (IX) complexes behave as field-induced SMM. The gadolinium(III) complexes can exhibit magnetic relaxation [ 56 , 57 , 58 , 59 , 60 ] either due to weak anisotropy [ 56 ] or a low rate of relaxation processes other than Orbach relaxation. The observed effect requires more thorough studies.…”

Identical Anomalous Raman Relaxation Exponent in a Family of Single Ion Magnets: Towards Reliable Raman Relaxation Determination?

“…4,32,33 Moreover, deep understanding of relaxation mechanisms for SIMs which do not possess pure mJ ground states is also important from the point of view of molecular qubit candidates design, demonstrated for several non-dysprosium complexes so far. [34][35][36][37][38][39][40] Herein we present a thorough magnetic and EPR study of three lanthanide-based SIMs from the family of [Ln(phendo)4](NO3)3•xMeOH (Ln = Gd (Gd), Er (Er), Yb (Yb), phendo = 1,10-phenanthroline-N,N'-dioxide). The complexes show four-bladed propeller-like geometry enforced by the helicene-type phendo ligands.…”