Large breathing effect induced by water sorption in a remarkably stable nonporous cyanide-bridged coordination polymer

Abstract

While metal-organic frameworks (MOFs) are at the forefront of cutting-edge porous materials, extraordinary sorption properties can also be observed in Prussian Blue Analogs (PBAs) and related materials comprising extremely short...

Magnetic interactions controlled by light in the family of Fe(ii)–M(iv) (M = Mo, W, Nb) hybrid organic–inorganic frameworks

“…Moreover, when the photo-irradiated Fe 2 Mo and Fe 2 W are heated to 240 K in order to reverse the photo-induced changes, the ground diamagnetic state of the octacyanidometallate( iv ) chromophores can be fully recovered only for Fe 2 W . This is in line with our previous studies of Mo IV /W IV photomagnetic assemblies 55,56 and may indicate better reversibility of the photomagnetic effects in octacyanidotungstate( iv )-based compounds.…”

“…This indicates that octacyanidotungstate( iv ) either shows better reversibility of the photo-induced transition or undergoes thermal relaxation in lower temperature range than the octacyanidomolybdate( iv ), which is in line with similar previous observations for {[Mn II (imH)] 2 [M IV (CN) 8 ]} n (M = Mo, W) compounds. 55,56…”

Crystal Engineering and Photomagnetic Studies of CN-Bridged Coordination Polymers Based on Octacyanidometallates(IV) and [Ni(cyclam)]2+

“…Moreover, for the first time we present the photomagnetic switching of octacyanidotungstate­(IV) and octacyanidomolybdate­(IV) photomagnetic chromophores embedded into the nickel­(II)-based coordination polymers ( 3 , 7 ). All previous examples involve other combinations of metal ions: Cu II –M IV (CN) 8 , , Zn II –M IV (CN) 8 , , Mn II –M IV (CN) 8 , , Fe II –M IV (CN) 8 , Cd II –M IV (CN) 8 , or Pt IV –M IV (CN) 8 (M = Mo, W). Similar to Mn II –M IV (CN) 8 coordination polymers, the photomagnetic response of M IV (CN) 8 moieties in the reported Ni II –M IV (CN) 8 frameworks is significantly stronger for the dehydrated phases as compared to the pristine ones.…”

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials

“…reported stepwise water adsorption in {[Mn(imH)] 2 [Mo(CN) 8 ]} n (1Mn; imH = imidazole) associated with large breathing effect. [ 36 ] Three well‐defined steps in water adsorption were found, corresponding to three different phases as determined by powder X‐ray diffraction studies ( Figure 6 a,b ). Upon dehydration, four free water molecules and one coordinated water molecules in the hydrated {[Mn(imH)(H 2 O) 2 ] 2 [Mo(CN) 8 ]·4H 2 O} n (1Mn·8H 2 O) were removed in the first step affording 1Mn 3H 2 O, followed by further dehydration on another coordinated water molecules in the second step, giving 1Mn 2H 2 O (Figure 6c ).…”