Spin-Crossover Iron(II) Coordination Polymer with Fluorescent Properties: Correlation between Emission Properties and Spin State

Abstract

A spin-crossover coordination polymer [Fe(L1)(bipy)] n (where L = a N 2 O 2 2– coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4′-bipyridine) was synthesized and exhibits a 48 K wide thermal hysteresis above room temperature ( T 1/2 ↑ = 371 K and T 1/2 ↓ = 323 K) that is stable for several cycles. The spin transition was characterized using magnetic measurements, Mössbauer spectroscopy, and DSC measurements. T -dependent X-ray powder diffraction reveals a structural phase transition coupled with the spin transition phenomenon. The dimeric excerpt {(μ-bipy)[FeL1(MeOH)] 2 }·2MeOH of the coordination polymer chain crystallizes in the triclinic space group P 1̅ and reveals that the packing of the molecules in the crystal is dominated by hydrogen bonds. Investigation of the emission properties of the complexes with regard to temperature shows that the spin crossover can be tracked by monitoring the emission spectra, since the emission color changes from greenish to a yellow color upon the low spin-to-high spin transition.