Photochromic substances have the characteristic of reversible change of color and various physical properties, in which the compounds whose magnetic properties change with light stimulation (that is, the so-called photo-magnetic effect) have the functions of strong photoprotection and optical switch of general photochromic substances. It may also play an important role in magnetic resonance imaging and optical information storage.

Polycyano coordination compounds are considered as the most promising materials of this kind and have attracted much attention for many years. However, their photo-magnetic effects usually occur below the liquid nitrogen temperature and are rare near room temperature. Therefore, it is of great scientific significance to develop photochromic polycyano coordination compounds with room-temperature magneto-optic effects.

The research team led by Guo Guocong, a researcher at the State Key Laboratory of Structural Chemistry of the Fujian Institute of Research on the Structure of Matter of the Chinese Academy of Sciences, has long been engaged in structural chemistry studies of inorganic-organic hybrid functional materials. In 2003, they reported the synthesis and crystal structure of [NdIII(DMF)4(H2O)3(u-CN)FeIII(CN)5]·H2O (NdFeDMF).

Later, two Japanese and Italian research teams found that the compound and other similar 3d-4f polycyano coordination compounds have novel photomagnetic effects, but the magneto-optical transition temperature is lower than 50K, and its underlying mechanism is still controversial. Recently, Guo Guocong and Wang Mingsheng’s research team have found that [EuIII(18-crown-6)(H2O)3]FeIII(CN)6·2H2O is UV-absorbed at room temperature under the support of the National Natural Science Foundation of China and the Natural Science Foundation of Fujian Province. After irradiation with light or violet light, the lone pair of electrons on the crown ether oxygen is transferred to trivalent iron to generate a stable crown ether radical and divalent iron. The crystal color changes from yellow-green to orange, and the discolored sample is in the darkened chamber. After standing or heating, it can fade, and then it can be re-illuminated to show typical photochromic phenomena. Before and after the discoloration, the magnetic properties of the compounds changed significantly. In this work, after the crystal powder was irradiated by a diode-pumped solid-state laser with a wavelength of 355 nm and a power density of 60 mW/cm2 for 10 minutes, the MT value at room temperature decreased by 33.5%, which was larger than the reported value of NdFeDMF (<3%). many.

This work has for the first time discovered the photochromism of 3d-4f polycyano complexes and the photomagnetic effect at room temperature. Not only has a photochromic material been successfully excavated from known compounds, but a class of room-temperature photocatalytic materials has also been developed. The light-induced valence tautomeric compounds of the magneto-optic effect have recently been published in the form of communication in J. Am. Chem. Soc. 2015, 137, 10882−10885.

Previously, the research team has made a series of advances in structural chemistry studies of inorganic-organic hybrid photochromies (Angew. Chem. Int. Ed., 2007, 46, 3269, 2008, 47, 3565, 2008, 47 , 4149, 2012, 51, 3432, 2014, 53, 9298, 2014, 53, 11529; Chem. Commun., 2010, 46, 361, review).

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