Issue 24, 2021

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.

Graphical abstract: Second harmonic generation on chiral cyanido-bridged FeII–NbIV spin-crossover complexes

Supplementary files

Article information

Article type
Paper
Submitted
22 Apr 2021
Accepted
24 May 2021
First published
26 May 2021

Dalton Trans., 2021,50, 8524-8532

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

S. Kawabata, K. Nakabayashi, K. Imoto, S. Klimke, F. Renz and S. Ohkoshi, Dalton Trans., 2021, 50, 8524 DOI: 10.1039/D1DT01324F

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