Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers
Bibliographic record
Abstract
The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.
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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".