Atomlike Building Units of Adjustable Character: Solid‐State and Solution Routes to Manipulating Hexanuclear Transition Metal Chalcohalide Clusters

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

“…[9,148] RheniumA C H T U N G T R E N N U N G (III) chalcogenide cluster cores survive such reagents: hexa-hydroxo clusters [Re 6 Q 8 (OH) 6 ] 2À (Q = S, Se) are prepared from the lamellar precursors Re 6 Q 8 Br 2 in molten KOH, [149 ] and cyanide-terminated [Re 6 Q 8 ] 2 + clusters (Q = S, Se, Te) are now legion. [150][151][152][153][154][155][156][157] The greater covalency of the rheniumA C H T U N G T R E N N U N G (III) chalcogenide core reinforces it structurally and opens a range of coordination chemistry not yet available to tungsten(II) or molybdenum(II) halide clusters.…”

“…Excited-state population of a metal-centered orbital was judged not inconsistent with the experimental photophysics of [Mo 6 X 8 X' 6 ] 2À and [W 6 X 8 X' 6 ] 2À species.A leading development in the chemistry of d 4 -metal atom clusters in the last 15 years has been the emergence of soluble rheniumA C H T U N G T R E N N U N G (III) chalcohalide clusters [Re 6 Q 8 X 6 ] 4À (Q = S, Se; X = Cl, Br, I). [66][67][68][69][70][71] These clusters are prepared in moderate yields from self-assembly reactions of noncluster precursors at elevated temperatures. Hexanuclear rheniumA C H T U N G T R E N N U N G (III) chalcogenide clusters also phosphoresce, [72][73][74][75][76][77][78][79][80] and the totality of Mo II , W II , and Re III clusters (Tc III analogues are known in the solid state [81,82] ) apparently constitute the biggest series of isoelectronic clusters known.…”

Reversible Electrochemical Lithium-Ion Insertion into the Rhenium Cluster Chalcogenide–Halide Re6Se8Cl2

“…Previous studies focused on the luminescent and electrochemical properties of the molecular [Re 6 Se 8 ] 2+ unit, − as well as using the cluster core as a building block to prepare materials for a variety of applications. − This investigation focuses on Re 6 Se 8 Cl 2 with the [Re 6 Se 8 ] 2+ cluster unit isostructural to that found in the superconducting Mo 6 Q 8 Chevrel-phase core . Theoretical and experimental studies have explored the ability of Chevrel-phase materials (Mo 6 S 8 ) to reversibly transfer four electron equivalents (ee) per formula unit. − Unlike the molybdenum analogue, the hexarhenium core has been studied as a “building unit” in extended solid frameworks, where motifs of three, two, and one dimensionality are possible. , These frameworks consist of rigid cluster–cluster linkages, some of which can undergo dimensional reduction in the presence of Cs + or Tl + halides.…”

Two-Dimensional Nanosheets from Redox-Active Superatoms

“…Our building blocks are atomically defined entities whose isolated electronic and redox properties can be incorporated into extended structures in which the structural element is preserved. Recent theoretical calculations have established that polynuclear Co 6 Se 8 L 6 clusters behave as “superatoms”. − We have previously used such superatoms to form solids from two different yet electronically complementary building blocks; directed-layer fullerene assemblies from phenanthrene-decorated clusters; and covalent assemblies through directed ligand exchange. − Redox-active M 6 E 8 clusters (M = Re, W; E = S, Se) have previously been functionalized with reactive ligands to generate frameworks of these preformed entities through cyanide and bipyridine coordination with transition metal ions. − Others have employed a variety of techniques to direct clusters and nanocrystals into extended lattices. − …”