Bibliographic record
Abstract
The focus of this thesis is the incorporation of the 1,2-bis(pyridinium)ethane motif into new [2]rotaxane ligands for the purpose of developing new metal organic rotaxane frameworks (MORFs). Both new stoppers that can act as ligands as well as new crown ethers with appended donors were synthesized and these components combined to create new [2]rotaxane ligands and eventually new MORFs. Chapter 2, looks at the synthesis and coordination chemistry of a [2]rotaxane containing terpyridine stoppers. The [2]rotaxane was shown to form mixed ligand complexes with RuII, AgI, ZnII, and PdII. The complexes were studied in solution by NMR, and UV/vis spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. Chapter 3 and 4, focuses on the synthesis of new tetrasubstituted dibenzo-24-crown-8 ethers and their inclusion into [2]pseudorotaxanes and [2]rotaxanes. The new [2]pseudorotaxanes and [2]rotaxanes were characterized in solution by NMR spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. The new crown ethers were then used for the development of [2]rotaxane ligands and metal organic rotaxane frameworks. The complexes were studied in solution by NMR, and UV/vis spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. Chapter 5, focuses on a new class of MORFs in which donor groups have been incorporated on to the crown ethers which allows for the [2]rotaxane ligands to link though the wheel rather than axles to propagate the coordination polymer. The highlight was formation of a coordination complex with CdII that is a 2-periodic, metal-organic rotaxane framework. The synthesis and characterization of all the species were studied by NMR spectroscopy and mass spectrometry in solution and in the solid state by X-ray crystallography. Chapter 6, looks at ways to combine chelating axles with coordinating crown ethers to form unique "combo" [2]rotaxane ligands capable of forming two independent frameworks by virtue of having coordinating groups on both components of the rotaxane. A new stopper based on a the polydentate ligand bis(2-pyridylmethyl)amine was developed for this purpose. "Combo" [2]rotaxane ligands were prepared and characterized in solution by NMR spectroscopy and mass spectrometry.
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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 | 0.001 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.008 | 0.001 |
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".