Single crystal-to-single crystal transformation – from two distinct to three distinct spin crossover centers in 2D coordination polymer [Fe(bbtr)3](CF3SO3)2

Abstract

1,4-Di(1,2,3-triazol-1-yl)butane (bbtr) forms a two-dimensional (2D) coordination polymer (1) in a reaction with iron(II) triflate. In the crystal lattice there are two crystallographically unique iron(II) ions surrounded octahedrally by a 1,2,3-triazole ring coordinated through nitrogen atoms N3. Single crystal X-ray diffraction studies revealed that spin crossover for each crystallographically independent iron(II) ion proceeds at a different temperature (T_1/2(Fe1) = 201 K; T_1/2(Fe2) = 216 K), while the magnetic measurements showed that there is one step, complete thermally induced spin crossover (T_1/2 = 205 K). Complex 1 undergoes, with time, single crystal-to-single crystal transformation (SCSC) to the converted system (1c) from the R to the P6₃ space group, accompanied by significant changes in the lattice parameter c (a shortening of approximately one-third) and consequently unit cell volume. Structural transformation is associated with rebuilding of the polymeric layer as well as the anion network, which is reflected in the results of Mössbauer studies. In the polymorphic system (1c) there are three crystallographically independent iron(II) ions. The temperature dependence results for magnetic susceptibility indicated complete, one-step spin crossover very similar to that of 1; however, single-crystal X-ray diffraction studies of 1c revealed that spin crossover for each crystallographically independent iron(II) ion occurs in a different manner, revealing three elementary stages (T_1/2(Fe1) = 200 K; T_1/2(Fe2) = 212 K, T_1/2(Fe3) = 214 K).