The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides

Abstract

One of the most exciting recent developments concerning molecular architectures is the emerging field of crystalline chalcogenide superlattices that bridges two traditional but distinct areas of research: chalcogenide clusters and porous materials. By combining synthetic and structural concepts in these two areas, many crystalline solids containing spatially organized chalcogenide clusters have been created that exhibit varied properties ranging from microporosity, fast ion conductivity, and photoluminescence to narrow and tunable electronic band gaps. The potential applications of these materials extend beyond traditional areas such as acid catalysis or adsorption-based separation to include shape- or size-selective photocatalysis, solid-state ionics, and electrochemistry.

Trigonal Bipyramidal Metalselenide Clusters with Palladium and Tin Atoms in Various Positions

“…The reaction of A with (SiMe 3 ) 2 1, 2, and 3 were analyzed by single-crystal X-ray diffraction (see Experimental Section and Supporting Information). The molecular structures of compounds 1-3 are shown in Figure 1.…”

“…[21] However, trigonal bipyramidal metal chalcogenide clusters, in which transition metal atoms are combined with tin atoms, are very rare. The only examples known to date are clusters of the general type [(ML z ) 2 [22] [Ru 3 (CO) 7 [23] Owing to the unsymmetrical coordination sphere at the Pd atoms, the Se-Pd distances vary much more distinctly than those in 1 and 2. Further, the replacement of one Pd atom by an [SnR 2 Cl 2 ] unit naturally causes a distortion of the bipyramid, which is reflected by more obtuse Se-Pd-Se angles of 80.58 (9) 2].…”

“…[1,2] Less attention has been paid to clusters that comprise a reactive organic ligand shell. However, as this generally allows for further extension of the cluster surface and attachment to solid substrates, one of our current aims is the synthesis and thorough investigation of metal chalcogenide clusters that comprise ligands with functional groups.…”

“…The only exceptions so far are the clusters [(R 4 Sn) 4 2 ; X = Cl, Br, I). [16] The combination of Pd with group 14 elements is known to be catalytically highly active in nanoparticles, for which this elemental combination caught our interest.…”

Synthesis and characterization of [Cd8Cl2Se(SePh)12(PCy3)2]·2.5CH3OH

“…[5][6][7] Our search for new metalchalcogen-containing building blocks is of great interest for many reasons, principally because the variable size of the blocks produces tunable optoeletronic properties of the bulk products, [8][9][10] This emerging field -super lattices of crystalline chalcogenideslinks two traditional, but distinct, areas of research: chalcogenide clusters and reticular materials. [11][12][13][14][15][16][17][18][19] Some authors have proposed alternative ways for the development of metal-chalcogenide clusters. Steigerwald and co-workers [20][21][22][23] have demonstrated the utility of trialkylphosphine tellurides (R 3 P = Te) as a source of soluble "Te(0)" to form numerous metal-telluride polynuclear complexes.…”