The preparative and materials chemistry of high nuclearity transition metal chalcogenide nanoclusters has been in the focus of our research for many years. These polynuclear metal compounds possess rich photophysical properties and can be understood as intermediates between mononuclear complexes and binary bulk phases. Based on our previous results we discuss herein recent advances in three different areas of cluster research. In the field of copper selenide clusters we present the synthesis of monodisperse, nanostructured α‐Cu2Se via the thermolysis of well‐defined cluster compounds as well as our approaches in the synthesis of functionalized clusters. In case of silver chalcogenides we established a strategy to synthesis cluster compounds containing several hundreds of silver atoms with the nanoclusters arranging in a closely packed crystal lattice. Finally the presented chalcogenide clusters of the group 12 metals (Zn, Cd, Hg) can be taken as model compounds for corresponding nanoparticles as even the smallest of frameworks display a clear structural relationship to the bulk materials.

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The reaction of [(3,5-Me(2)-C(5)H(3)N)(2)Zn(ESiMe(3))(2)] (E = Se, Te) with cadmium(II) acetate in the presence of PhESiMe(3) and P(n)Pr(3) at low temperature leads to the formation of single crystals of the ternary nanoclusters [Zn(x)()Cd(10)(-)(x)()E(4)-(EPh)(12)(P(n)()Pr(3))(4)] [E = Se, x = 1.8 (2a), 2.6 (2b); Te, x = 1.8 (3a), 2.6 (3b)] in good yield. The clusters [Zn(3)Hg(7)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (4) and [Cd(3.7)Hg(6.3)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (5) can be accessed by similar reactions involving [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SeSiMe(3))(2)] or [(N,N'-tmeda)Cd(SeSiMe(3))(2)] (1) and mercury(II) chloride. The metal silylchalcogenolate reagents are efficient delivery sources of {ME(2)} in cluster synthesis, and thus, the metal ion content of these clusters can be readily moderated by controlling the reaction stoichiometry. The reaction of cadmium acetate with [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SSiMe(3))(2)], PhSSiMe(3), and P(n)()Pr(3) affords the larger nanocluster [Zn(2.3)Cd(14.7)S(4)(SPh)(26)(P(n)()Pr(3))(2)] (6). The incorporation of Zn(II) into {Cd(10)E} (E = Se, Te) and Zn(II) or Cd(II) into {Hg(10)Se} nanoclusters results in a significant blue shift in the energy of the first "excitonic" transition. Solid-state thermolysis of complexes 2 and 3 reveals that these clusters can be used as single-source precursors to bulk ternary Zn(x)Cd(1)(-)(x)E materials as well as larger intermediate clusters and that the metal ion ratio is retained during these reactions.

Reaction of lithium phenylselenothiolate, generated in situ from the reductive cleavage of PhSe-SiMe 3 with alkyl lithium reagents and insertion of elemental sulfur, with triphenylphosphine solubilized CuCl affords the molecular cluster complex [Cu 20 Se 4 -(µ 3 -SePh) 12 (PPh 3 ) 6 ] (1). The analogous reaction with AgCl yields the extended structure [Ag(SePh)] ϱ (2) in which an infinite layer of Ag I atoms is capped on either side by µ 4 -SePh ligands. Synthese und strukturelle Charakterisierung von [Cu 20 Se 4 (µ 3 -SePh) 12 (PPh 3 ) 6 ] und [Ag(SePh)] ؕInhaltsübersicht. Die Reaktion von Lithiumphenylselenothiolat, in situ durch reduktive Spaltung von PhSeϪSiMe 3 mit LithiumalkylReagenzien und Insertion elementarem Schwefel gebildet, mit in Triphenylphosphan gelöstem CuCl ergibt den molekularen Clusterkomplex [Cu 20 Se 4 (µ 3 -SePh) 12 (PPh 3 ) 6 ] (1). Die analoge Reaktion mit AgCl ergibt [Ag(SePh)] ϱ (2) mit einer unendlichen Schicht von