Monitoring Fe(II) Spin-State Equilibria via Eu(III) Luminescence in Molecular Complexes: Dream or Reality?

The modulation of light emission by Fe(II) spin-crossover processes in multifunctional materials has recently attracted major interest for the indirect and noninvasive monitoring of magnetic information storage. In order to approach this goal at the molecular level, three segmental ligand strands, L4-L6, were reacted with stoichiometric mixtures of divalent d-block cations (M(II) = Fe(II) or Zn(II)) and trivalent lanthanides (Ln(III) = La(III) or Eu(III)) in acetonitrile to give C₃-symmetrical dinuclear triple-stranded helical [LnM(Lk)₃]⁵⁺ cations, which can be crystallized with noncoordinating counter-anions. The divalent metal M(II) is six-coordinate in the pseudo-octahedral sites produced by the facial wrapping of the three didentate binding units, the ligand field of which induces variable Fe(II) spin-state properties in [LnFe(L4)₃]⁵⁺ (strictly high-spin), [LnFe(L5)₃]⁵⁺ (spin-crossover (SCO) around room temperature), and [LnFe(L6)₃]⁵⁺ (SCO at very low temperature). The introduction of the photophysically active Eu(III) probe in [EuFe(Lk)₃]⁵⁺ results in europium-centered luminescence modulated by variable intramolecular Eu(III) → Fe(II) energy-transfer processes. The kinetic analysis implies Eu(III) → Fe(II) quenching efficiencies close to 100% for the low-spin configuration and greater than 95% for the high-spin state. Consequently, the sensitivity of indirect luminescence detection of Fe(II) spin crossover is limited by the resulting weak Eu(III)-centered emission intensities, but the dependence of the luminescence on the temperature unambiguously demonstrates the potential of indirect lanthanide-based spin-state monitoring at the molecular scale.