Synthesen und Kristallstrukturanalysen der Ag‐S‐Cluster [Ag₇₀S₂₀(SPh)₂₈(dppm)₁₀](CF₃CO₂)₂ und [Ag₂₆₂S₁₀₀(StBu)₆₂(dppb)₆]

Synthesis and Structure of [Ag26In18S36Cl6(dppm)10(thf)4][InCl4(thf)]2—A Combined Approach of Theory and Experiment

“…The shortest separation of silver atoms in 1 is found to be 282.3 pm (Ag12-Ag12'), which is comparable with metal-metal distances in other silver sulfide complexes and clusters considered to be nonbonding. [5,6,15] Common values were also found for the AgÀP bond lengths, which range from 237.5(3) pm to 250.0(3) pm.…”

“…[2] The driving force of this reaction is the formation of XSiMe 3 . In this way, a large number of cluster compounds have been synthesized and structurally characterized, for example, [Cu 146 Se 72 (PPh 3 ) 30 ], [3] [Ag 172 Se 40 -(SenBu) 92 dppp] (dppp = bis(diphenylphosphanyl)propane), [4] [Ag 188 S 94 (PR 3 ) 30 ] (R= nPr, nBu) [5] and [Ag 262 S 100 (StBu) 62 (dppb) 6 ] (dppb = bis(diphenylphosphanyl)butane). [6] Calculations reveal that the PR 3 -stabilized cluster complexes are metastable intermediates on the way to forming the corresponding binary phases.…”

“…In this way, a large number of cluster compounds have been synthesized and structurally characterized, for example, [Cu 146 Se 72 (PPh 3 ) 30 ], [3] [Ag 172 Se 40 -(SenBu) 92 dppp] (dppp = bis(diphenylphosphanyl)propane), [4] [Ag 188 S 94 (PR 3 ) 30 ] (R= nPr, nBu) [5] and [Ag 262 S 100 (StBu) 62 (dppb) 6 ] (dppb = bis(diphenylphosphanyl)butane). [6] Calculations reveal that the PR 3 -stabilized cluster complexes are metastable intermediates on the way to forming the corresponding binary phases. [7] Ternary compounds, however, offer a broader spectrum of tunable properties and are viable candidates for technical use, for example, CuInSe 2 is one of the most promising materials for thin-film technology in solar cells, [8] and conversion efficiencies of up to 18.8 % have been achieved with Cu(In,Ga)Se 2 under laboratory conditions; [9] AgInS 2 , AgIn 5 S 8, and AgGaS 2 are of interest as materials for non-linear optical devices.…”

“…[10] This prompted us to investigate the synthesis of ternary cluster compounds composed of elements of Group 11,13,and 16. Similar to the synthetic approach for binary clusters outlined above, the reaction of mixtures of the metal halides with E(SiMe 3 ) 2 6 ], (M = Cu, Ag; M' = Ga, In; E = S, Se). [11,13] Interestingly, the stoichiometric composition and structure of the cluster molecules differ from the corresponding bulk material.…”

New Copper Chalcogenide Clusters with a Selenide Core and a Sulfide Shell

“…[4][5][6] In the corresponding field of binary-ligand-protected cluster compounds a large number of species have been synthesized and structurally characterized by single-crystal Xray analysis. [7,8] In these systems the size regime of the larger clusters overlaps with the size regime of the smaller nanoparticles (having diameters of 1-3 nm). An investigation of a series of different sized cadmium selenide clusters has shown that their absorption properties are mainly dominated by the metal chalcogenide core, whereas the very weak fluorescence is due to processes in the organic ligand shell.…”