Second harmonic generation on chiral cyanido-bridged FeII-NbIV spin-crossover complexes.

Abstract

Incorporating chiral organic ligands into cyanido-bridged FeII-NbIV assemblies synthesized chiral spin-crossover complexes, FeII2[NbIV(CN)8](L)8·6H2O (L = R-, S-, or rac-1-(3-pyridyl)ethanol: R-FeNb, S-FeNb, or rac-FeNb). Rietveld analyses based on a racemic complex of rac-FeNb indicate that the chiral complexes have a cubic crystal structure in the I213 space group with a three-dimensional cyanido-bridged FeII-NbIV coordination network. All the complexes exhibit spin crossover between the high-spin (HS) and the low-spin (LS) FeII states without thermal hysteresis. Chiral complexes of R-FeNb and S-FeNb show second harmonic generation (SHG) due to their non-centrosymmetric structure. The I213 space group provides second-order susceptibility tensor elements of χxyz, χyzx, and χzxy, which contribute to SHG. The temperature-dependent second harmonic light intensity change is due to spin crossover between FeIIHS and FeIILS.