Characterization of A_x[W₆I₁₄] as Key Compounds for Ligand‐Substituted A₂[W₆I₈L₆] Clusters

Abstract

A x [W 6 I 14 ] compounds with A = Na, K, Rb, or Cs are prepared from W 3 I 12 and alkali iodides (AI). Crystal structures were solved and refined for Na[W 6 I 14 ] and A 2 [W 6 I 14 ] compounds with A = K, Rb and Cs on the basis of powder and single-crystal XRD diffraction. All compounds behave stable in air and can be dissolved in polar organic solvents making them [a]

Preparation and Luminescence of Cluster Compounds [W6Br8L6]2– with L = CF3COO and C7H7SO3

“…[25,34] A comparison of our results on bromides with the corresponding iodides reveals blue shifted emission wavelengths (λ em,max ) of the respective iodide compounds by 75 and 52 nm.…”

Ligand Influence on the Photophysical Properties and Electronic Structures of Tungsten Iodide Clusters

“…The preparation of the new compound (TBA) 2 [W 6 I 8 (O 3 SC 7 H 7 ) 6 ] [TBA = ( n‐ C 4 H 9 ) 4 N] was investigated. For this purpose, we departed from W 3 I 12 , which reacts with CsI to produce Cs 2 [W 6 I 14 ] . The (TBA) 2 [W 6 I 14 ] derivative is an orange crystalline powder, which can be dissolved in polar organic solvents.…”

“…The chemicals used were obtained from commercial suppliers and used without further purification. The syntheses of Cs 2 [W 6 I 14 ] and (TBA) 2 [W 6 I 14 ] were performed by literature procedures.…”

Molybdenum Iodides – from Obscurity to Bright Luminescence

“…Preparation of Cs 2 [W 6 I 14 ] from W 3 I 8 · 2I 2 and CsI at 550 °C can be recommended as alternative. Similar reaction with KI and RbI yields the K + and Rb + salts, whereas with NaI the product was Na[{W 6 I 8 }I 6 ] with 23 cluster skeleton electrons …”

“…The catalyst composition is given as {[Mo 6 I 8 (OOCC 6 H 4 PPh 2 ) 5.4 (OOCC 6 H 4 P(O)Ph 2 ]Pd II Pd 0 0.6 } . Na 2 [{W 6 I 8 }(OMe) 6 ] was prepared from Na[{W 6 I 8 }I 6 ] with excess NaOMe in methanol . Note the reduction of the electron‐deficient {W 6 I 8 } 5+ core into electron‐precise {W 6 I 8 } 4+ core in this apparently simple reaction …”