Controlled Synthesis of Ternary II−II‘−VI Nanoclusters and the Effects of Metal Ion Distribution on Their Spectral Properties
Bibliographic record
Abstract
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.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".