Degroot Marty W, Taylor Nicholas J, Corrigan John F
Departments of Chemistry, The University of Western Ontario, London, Canada N6A 5B7, and University of Waterloo, Waterloo, Canada N2L 3G1.
Inorg Chem. 2005 Jul 25;44(15):5447-58. doi: 10.1021/ic0481576.
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.
在低温下，[(3,5-二甲基环戊二烯基)₂Zn(ESiMe₃)₂]（E = Se，Te）与醋酸镉在PhESiMe₃和三正丙基膦存在下反应，能高产率地生成三元纳米簇[ZnₓCd₁₀₋ₓE₄-(EPh)₁₂(P(n)Pr₃)₄]的单晶[E = Se，x = 1.8 (2a)，2.6 (2b)；Te，x = 1.8 (3a)，2.6 (3b)]。通过涉及[(3,5-二甲基环戊二烯基)₂Zn(SeSiMe₃)₂]或[(N,N'-四甲基乙二胺)Cd(SeSiMe₃)₂]（1）与氯化汞的类似反应，可以得到簇合物[Zn₃Hg₇Se₄(SePh)₁₂(P(n)Pr₃)₄]（4）和[Cd₃.₇Hg₆.₃Se₄(SePh)₁₂(P(n)Pr₃)₄]（5）。金属硅基硫属化合物试剂在簇合物合成中是{ME₂}的有效供应源，因此，通过控制反应化学计量比，可以很容易地调节这些簇合物中的金属离子含量。醋酸镉与[(3,5-二甲基环戊二烯基)₂Zn(SSiMe₃)₂]、PhSSiMe₃和三正丙基膦反应，得到更大的纳米簇[Zn₂.₃Cd₁₄.₇S₄(SPh)₂₆(P(n)Pr₃)₂]（6）。将Zn(II)掺入{Cd₁₀E}（E = Se，Te）以及将Zn(II)或Cd(II)掺入{Hg₁₀Se}纳米簇中，会导致第一个“激子”跃迁能量发生显著蓝移。配合物2和3的固态热解表明，这些簇合物可用作块状三元ZnₓCd₁₋ₓE材料以及更大的中间簇合物的单源前驱体，并且在这些反应过程中金属离子比例得以保留。
