Spin crossover metal-organic frameworks with inserted photoactive guests: on the quest to control the spin state by photoisomerization

• Published in: Dalton transactions : an international journal of inorganic chemistry 2021-06, Vol.5 (25), p.8877-8888
• Main Authors: Brach aková, Barbora, Monco, Ján, Pavlik, Ján, Šalitroš, Ivan, Bonhommeau, Sébastien, Valverde-Muñoz, Francisco Javier, Salmon, Lionel, Molnár, Gábor, Routaboul, Lucie, Bousseksou, Azzedine
• Format: Article
• Language: English
• Subjects: Acetylene; Azo compounds; Chemical Sciences; Chemical synthesis; Coordination chemistry; Cristallography; Crystallography; Crystals; Electron spin; Iron; Metal-organic frameworks; Single crystals; Stilbene; Thermogravimetry; X ray powder diffraction; X-ray diffraction
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt01057c

Three Hofmann-like metal-organic frameworks {Fe(bpac)[Pt(CN) 4 ]}·G (bpac = 1,2-bis(4-pyridyl)acetylene) were synthesized with photoisomerizable guest molecules (G = trans -azobenzene, trans -stilbene or cis -stilbene) and were characterized by elemental analysis, thermogravimetry and powder X-ray diffraction. The insertion of guest molecules and their conformation were inferred from Raman and FTIR spectra and from single-crystal X-ray diffraction and confronted with computational simulation. The magnetic and photomagnetic behaviors of the framework are significantly altered by the different guest molecules and different conformations. On the other hand, photoisomerization of the guest molecules becomes strongly hindered by the framework. The introduction of photoactive guest molecules into a spin crossover 3D metal organic framework alters the switchable properties of both host and guest.