Aza‐Diphosphazenanes: Inorganic Cyclohexane‐like Connectors with Stereochemically Tunable Exit Vectors for Molecular and Macromolecular Chemistry
Bibliographic record
Abstract
Abstract Molecules that place functional groups at well‐defined angular and radial separations are valued as connectors in synthetic chemistry. Examples include rigid, polyvalent arenes and bicyclic compounds featuring strong C─C or C─H bonds. Aliphatic rings are rare in this context due to the challenge of stereochemical control over C─H functionalization. Here we investigate inorganic cyclohexane‐like P2N4 rings (aza‐diphosphinanes) and develop a model based on negative hyperconjugation and diaxial strain to explain their cis/trans isomerization. Informed by this model, we rationally make 1,4‐disubstituted aza‐diphosphinanes, and stereoselectively oxidize them to aza‐diphosphazenanes, which retain their cis (77°) or trans (180°) covalent exit vectors. These compounds show high stability but nevertheless react as 1,4‐dinucleophiles, supporting their classification as new cyclohexane‐like connectors. Appropriate connector choice in polycondensations enables the divergent synthesis of low‐molecular weight macrocyclic oligomers (from the cis variant) or the first example of high molecular weight cyclo‐linear polyphosphazenes (from the trans variant). These results provide fundamental insight into the stereochemistry of inorganic heterocycles and molecular dimensionality, debut connectors that fill a niche left by organic ones, and offer access to new classes of inorganic polymers for future investigation.
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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) | 0.002 | 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".