Lithium and Sodium Ion Distributions in A_2–x[W₆I₁₄] Structures

Abstract

Ag[WI] and A[WI] compounds with A = Na, Li were prepared from binary tungsten iodides (WI) and corresponding metal iodides. Their crystal structures are analyzed on the basis of X-ray diffraction data. Li andNa solid-state NMR measurements reveal that Li and Na ions are distributed over two sites in the respective structures. These results shed some new light on A [MI] with A = alkali and M = Mo, W compounds being reported with x = 1 and 2, which exhibit photophysical properties. The lithium compound is an exception in the series of A[WI] compounds, because it is the only compound which is soluble in water.

Alkaline Earth Cluster Compounds AE[W6I14] and the Solvate [Ca(C2H6SO)6][W6I14]

“…X‐ray powder diffraction (XRPD) studies on products from both reaction ways (solution and solid state) confirm the identity of corresponding AE [W 6 I 14 ] products, revealing that the synthesis via solution is a significant progress, respectively simplification for such reactions. Surprisingly, crystalline products from both reaction pathways appear with dark green body colour, as has been observed for A 2– x [W 6 I 14 ] with A = Li, Na …”

“…( n Bu 4 N) 2 [W 6 I 14 ] and other compounds based on the [W 6 I 14 ] 2– clusters represent prominent materials for optical properties (luminescence, singlet oxygen production) , . Alkali compounds A 2 [W 6 I 14 ] have shown poor luminescence properties in solid state, due to their dark body colors , . The same problem appears for AE [W 6 I 14 ].…”

“…Binary tungsten iodide clusters have been intensively studied over the last decades because of their promising properties . Among them, ternary salts with the octahedral tungsten iodide cluster [W 6 I 14 ] 2– were reported with alkaline elements ( A ) as A 2 [W 6 I 14 ] or cation deficient A 2– x [W 6 I 14 ] derivatives , . These compounds with the isolated [W 6 I i 8 I a 6 ] 2– (i = innen or inner and a = außen or outer) cluster are considered as useful starting materials for the preparation of cation substituted compounds ( n Bu 4 N) 2 [W 6 I 14 ], which allow high solubility in organic solvents.…”

“…[1] Among them, ternary salts with the octahedral tungsten iodide cluster [W 6 I 14 ] 2were reported with alkaline elements (A) as A 2 [W 6 I 14 ] or cation deficient A 2-x [W 6 I 14 ] derivatives. [2,3] These compounds with the isolated [W 6 I i 8 I a 6 ] 2-(i = innen or inner and a = außen or outer) cluster are considered as useful starting materials for the preparation of cation substituted compounds (nBu 4 N) 2 [W 6 I 14 ], [4] which allow high solubility in organic solvents. This compound can be then utilized in the preparation of ligand exchanged clusters, such as (nBu 4 N) 2 [W 6 I 8 (O 3 S 2 C 7 H 7 ) 6 ], which are showing enhanced luminescence properties including high singlet oxygen quantum yields.…”

Synthesis of (TeI3)2[W6I14] via Iodination of WTe2

“…Metal halide clusters with the octahedral [M 6 X 8 ] cluster core are evidenced by the binary compounds Mo 6 X 12 and W 6 X 12 ( X = Cl, Br, I) . Many compounds with the [W 6 I 14 ] 2– cluster have been developed with alkali as A 2 [W 6 I 14 ], and alkaline earth ions as ( AE )[W 6 I 14 ]. Their counterparts with organic cations like ( n Bu 4 N) +[8] can serve as soluble starting materials for the preparation of ligand substituted cluster compounds with the [W 6 I 8 L 6 ] 2– ion ( L is an inorganic or organic ligand) .…”