A Known Iron(II) Complex in Different Nanosized Particles: Variable-Temperature Raman Study of Its Spin-Crossover Behavior

The spin-crossover (SCO) polymorph B (complex 1) of the known compound [Fen(II)(CN)(2)}(2)(abpt)(2)], where abpt is 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole, has been prepared in three different particle sizes averaging similar to 300 (sample la), similar to 80 (sample lb), and similar to 20 nm (sample 1c). Two independent octahedral molecules possessing Fe1 and Fe2 were found to be present in the crystal of B. Magnetostructural relationships had established that at room temperature both Fe-II sites are in the high-spin state (HS-HS), whereas a decrease in the temperature to 90 K induces the complete high-spin to low-spin conversion of the Fe1 site, with Fe2 remaining in the high-spin state (LS-HS). The three samples have been characterized by elemental analyses, ATR spectra, solution UV/vis spectra (to exclude resonance Raman effects) and powder X-ray diffraction patterns, while their morphological characteristics have been examined by scanning electron microscopy (SEM). The SCO behavior of the originally prepared sample la has been monitored in detail by variable-temperature Raman studies in the 300-80 K range using mainly low-frequency upsilon(Fe N) and delta(NFeN) modes and the upsilon(C N) mode of the axial dicyanamido groups as spin-sensitive vibrations. The new peaks that appear in the low-temperature Raman spectra of the LS-HS form of the complex are reproduced in the calculated spectrum of the LS state of [Fe-II{N(CN)(2)}(2)(abpt)(2)]. The influence of the average particle size on the SCO properties of 1 has also been studied by variable-temperature Raman spectra. The studies indicate that, during the HS-HS -> LS-HS transition, the latter form of the complex appears at higher temperatures for the smaller particles; the T-1/2 shift accomplished by manipulating the particle size within a range of roughly 1 order of magnitude (300-20 nm) may be as high as similar to 30 K. The SCO features of 1, as deduced from the Raman study, are in excellent agreement with those derived from a traditional variable-temperature magnetic susceptibility study, indicating the utility of the former.