Octacyanidometallates for multifunctional molecule-based materials

Abstract

Diverse functional potential of heterometallic systems based on octacyanidometallates places them at the forefront of research into modern molecule-based materials.

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

“…39 Overcoming this stereotype is crucial for further progress in the field of multifunctional molecular materials as CN-CPs offer the possibility of fine tuning of many different functionalities including magnetism or magnetic and photomagnetic switching upon solvent removal/exchange. [40][41][42][43][44][45][46][47] This in turn will potentially lead to ground-breaking magnetic sponge systems 48,49 operational at room temperature.…”

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

“…As far as we know, 1Mn and {[Mn II (imH)]2[W IV (CN)8]}n constitute the first examples of isostructural octacyanometalate(IV)-based photomagnets in which both Mo IV and W IV congeners demonstrate photo-induced magnetic ordering. 41 This enables comparison of their photomagnetic functionalities, with the former responding to light even in the case of the fully hydrated network and the latter demonstrating higher magnetic ordering temperature and better reversibility of the photomagnetic effect.…”

“…39 Overcoming this stereotype is crucial for further progress in the field of multifunctional molecular materials as CN-CPs offer the possibility of fine tuning of many different functionalities including magnetism or magnetic and photomagnetic switching upon solvent removal/exchange. [40][41][42][43][44][45][46][47] This in turn will potentially lead to ground-breaking magnetic sponge systems 48,49 operational at room temperature.…”

Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4–/3–: Preparation of Homoleptic, Eight-Coordinate Methyl Isocyanide Complexes [W(CNMe)8]4+/5+

“…12 In contrast, octacyanometalates [M(CN)8] 4−/3− (M= Mo, W) have been frequently used as building blocks in coordination chemistry. 13 Most relevant are their applications in magnetochemistry, 14 for example for the preparation of photomagnetic materials 15 and single-molecule magnets. 16 Since octacyanometallates [M(CN)8] 4−/3− (M = Mo, W) are known, the question arises whether it could be possible to synthesize the fully alkylated complexes with eight isocyanide ligands, as Unfortunately, he was not able to determine the correct structure due to the lack of suitable spectroscopic methods.…”

“…Furthermore, the chemical shift of the main signal was almost identical to the corresponding triflate salt ( = 3.85 ppm).13 C NMR chemical shifts of the methyl group ( = 31.8 ppm) and the isocyanide carbon ( = 115.3 ppm) were assigned from the 13 C HMQC and 13 C HMBC spectra. Comparison of NMR shifts from cyanometalates and isonitrile complexes in ppm.13 C & 1 H relative to TMS in CDCl3 and14 N & 15 N relative to liquid NH3.…”