A repeatable bidirectional paramagnetic ↔ diamagnetic
photomagnetic
effect has been observed in the cyanide-bridged Fe–Co square
complex {[Fe{B(pz)4}(CN)3]2[Co(bik)2]2}(ClO4)2·3H2O [B(pz)4 = tetrapyrazolylborate, bik = bis(1-methylimidazol-2-yl)ketone].
Magnetic measurements and low-temperature single-crystal X-ray diffraction
experiments have shown that a complete electron transfer from the
diamagnetic FeII −Co III state to the
paramagnetic FeIII −Co II metastable
state is induced by 808 nm laser light irradiation, whereas the diamagnetic
state is recovered in an almost quantitative yield under irradiation
at 532 nm.
The self-assembly of [Fe(III)(Tp)(CN)(3)](-) and [Fe(II)(bik)(2)(S)(2)](2+) affords the cyanide-bridged mixed valence {Fe(III)(2)Fe(II)(2)}(2+) molecular square, which exhibits a photomagnetic effect under laser light irradiation at low temperature and also shows thermal spin-state conversion near ambient temperature.
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