Humidity‐Induced Switching between Two Magnetic and Structural Phases in a Co^II‐[W^V(CN)₈] Molecular Magnet

Abstract

The self-assembly of cobalt(II) with purine and octacyanidotungstate(V) resultsi nt he formation of the threedimensional Co 3 [W(CN) 8 ] 2 (purine) 2 ·8.5H 2 O( 1)c oordination polymer.T his compound exhibits humidity-inducedv ariation of the number of water molecules of crystallisation leading to ar eversible structuralp hase transition and the alternation of the long-range ferromagnetic ordering temperature from T C = 29 Kf or the pristine assembly (1)t oT C = 49 Kf or the sample stored in al ow-humidity atmosphere (1-deh). This phenomenon can be attributed to ar eversible change in the hydrogen-bonding network resulting in the modification of the local geometrieso fc obalt(II) as well as the cyanido bridges.

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

“…The unit cell volume per formula unit changes from 996 Å 3 in 1Mn to 1332 Å 3 in 1Mn•8H2O, which accounts for the 34% total change between the anhydrous and the fully hydrated phases, respectively. Such tremendous unit cell expansion is unprecedented among other porous cyanide-bridged polymers 46,[76][77][78][79][80][81][82][83][84] and falls within the range observed for flexible MOFs 52 . Interestingly, the structure of the anhydrous 1Mn does not show any solvent accessible voids and hence -no permanent porosity.…”

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

“…The unit cell volume per formula unit changes from 996 Å 3 in 1Mn to 1332 Å 3 in 1Mn•8H 2 O, which accounts for the 34% total change between the anhydrous and the fully hydrated phases, respectively. Such tremendous unit cell expansion is unprecedented among other porous cyanide-bridged polymers 46,[84][85][86][87][88][89][90][91][92] and falls within the range observed for flexible MOFs (Table 2). Interestingly, the structure of the anhydrous 1Mn does not show any solvent accessible voids and hence -no permanent porosity.…”

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

“…The unit cell volume per formula unit changes from 996 Å 3 in 1Mn to 1332 Å 3 in 1Mn•8H2O, which accounts for the 34% total change between the anhydrous and the fully hydrated phases, respectively. Such tremendous unit cell expansion is unprecedented among other porous cyanide-bridged polymers 46,[76][77][78][79][80][81][82][83][84] and falls within the range observed for flexible MOFs 52 . Interestingly, the structure of the anhydrous 1Mn does not show any solvent accessible voids and hence -no permanent porosity.…”