Emissive Ln(III)–Hg(II)/Pb(II) Coordination Polymers with Heteropolymeric 1-D Structures Synthesized Mechanochemically Using a Hard–Soft Acid–Base Mismatch Strategy
Bibliographic record
Abstract
The mechanochemical synthesis of a family of heterobimetallic Ln(III)-M(II) coordination polymers of the form [Ln(OAc) 2 (OH 2 ) 3 ](MBr 3 )]· x H 2 O (Ln = Eu, Tb, 50:50 Eu/Tb; LnHg: M = Hg, x = 1; LnPb: M = Pb, x = 0) is described. They are formed via the anion–exchange reaction between lanthanide(III) bromide and metal(II) acetate salts and driven by a mismatch in hard–soft acid–base character. The crystal structure of EuHg revealed a heteropolymeric 1-D structure, with cationic acetate-bridged and anionic bromide-bridged chains forming parallel arrays; IR, Raman, and photoluminescence spectroscopic data of LnPb strongly suggested similarity with the LnHg compounds. The analogous reaction with EuCl 3 ·6H 2 O and Hg(OAc) 2 forms an isostructural material, but substituting Pb(OAc) 2 generates [Eu(OAc) 2 (OH 2 ) 3 ]Cl and PbCl 2 instead of a mixed-metal product comparable to LnPb . An N, N -dimethylformamide (DMF) solvate [Eu(OAc) 2 (DMF) 3 ](PbBr 3 )] ( EuPb·DMF ) was structurally characterized, showing the same heteropolymeric motif as EuHg and resembling an organic–inorganic lead-halide perovskite due the anionic chain of face-sharing bromoplumbate(II) octahedra. Photoluminescence properties of the compounds, including lifetime measurements and Tb(III)→Eu(III) energy transfer parameters for the LnM 50:50 Eu/Tb solid-solutions are described.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 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) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".