Abstract
Compared with the ripple of visible EuIII-based emission intensity induced by appended [FeIIN6] spin crossover (SCO) units, as detected in the triple-stranded [EuFe(L1)3]5+ helicate, the lanthanide-based luminescent detection of FeII spin-state equilibria could be improved significantly if the luminophore emission is shifted toward the near-infrared (NIR) domain. Replacing EuIII with NdIII in [NdFe(L1)3]5+ (i) maintains the favorable SCO properties in acetonitrile [critical temperature T1/2 = 322(2) K], (ii) saturates nonradiative vibrational relaxation processes in the 233-333 K range, and (iii) boosts the crucial intramolecular NdIII → FeII energy transfer rate processes, which are sensitive to the spin state of the FeII metallic center. Consequently, the steady-state NIR Nd(4F3/2 → 4IJ) emission of the luminophore is amplified and linearly correlated with the low-spin-[FeIIN6] and high-spin-[FeIIN6] mole fractions controlled by the SCO equilibrium. This paves the way for a straightforward and direct NIR luminescent reading/sensing of the FeII spin state in single molecules.
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