Komplexe Flüssigkeiten der flexiblen, eindimensionalen Mineralpolymere [K(MPS4)]∞ (M=Ni, Pd): Selbstfragmentierung zum konkaven, cyclischen Thiophosphat (PPh4)3[(NiPS4)3]

Abstract

Eine bemerkenswerte Sequenz aus Selbstfragmentierung und Umlagerung führt beim Auflösen des Kaliumsalzes des geladenen Mineralpolymers ∞1[NiPS4]− in DMF zur unerwarteten Bildung des konkaven, cyclischen anorganischen Anions [(NiPS4)3]3− (rechts ist die Struktur, unten in Polyederdarstellung, gezeigt). Die so erhaltene komplexe Flüssigkeit weist eine transiente anisotrope Textur auf. In der Lösung von ∞1[PdPS4]− liegen dagegen bis 323 K stabile flexible, geladene Ketten vor.

Organized Nanostructured Complexes of Inorganic Clusters and Surfactants That Exhibit Thermal Solid‐State Transformations

“…To confirm the switch between crown and polymer in these materials, we studied the system showing the most marked changes, that is the [Ni 3 P 3 S 12 ] 3− /DiC 12 DA system by 31 P NMR spectroscopy (see reference 24 and 27 for more details). Solution‐state 31 P NMR spectra were recorded on freshly prepared deuterated DMF solutions from freshly prepared inorganic materials, and from the same materials heated to and kept at 100 °C for 4 h. Short acquisition times were used to ensure exclusion, as far as possible, of all possible degradation reactions and of formation of side products.…”

“…KMPS 4 compounds (M=Pd or Ni) were synthesized as described elsewhere 25, 26. A dark brown solution of the [Ni 3 P 3 S 12 ] 3− crown was obtained after dissolution of fine crystals of KNiPS 4 in DMF (65.5 mmol L −1 ) and heating for one week at 50 °C under stirring 24. Insoluble components were removed by filtration.…”

“…Elemental analysis (N, S) indicated that the 1:1 charge ratio of complexation was fulfilled and excluded the presence of free surfactant or uncomplexed inorganic cluster in the solid precipitate. (PPh 4 ) 3 [Ni 3 P 3 S 12 ] crystals were synthesized as described elsewhere24 as a reference compound.…”

“…Herein we employ the ISA route to generate nanostructured organic/inorganic hybrid materials with switchable structures from a special inorganic oligoelectrolyte species, the trimetallic concave cyclic anion [Ni 3 P 3 S 12 ] 3− ( 1 ) with pseudo‐ C 3v symmetry. This species is obtained from the autofragmentation/rearrangement of the inorganic polymer $\rm{^{1}_{\infty }}$ [NiPS 4 ] − in dimethylformamide (DMF) at 50 °C 24. The synthesis25, 26 and properties24, 27 of the polymer are described in detail elsewhere.…”

“…This species is obtained from the autofragmentation/rearrangement of the inorganic polymer $\rm{^{1}_{\infty }}$ [NiPS 4 ] − in dimethylformamide (DMF) at 50 °C 24. The synthesis25, 26 and properties24, 27 of the polymer are described in detail elsewhere. This bowl‐shaped cyclic anion 1 , whose charges are mainly localized on the three single‐bonded outer sulfur atoms,27 appears to be a good candidate to form mesophases by the ISA route with charged surfactants.…”