A Shape‐Complementarity Approach to Inducing Short Au(III)···Au(III) Contacts in Tetracyanoaurate(III) Salts
Bibliographic record
Abstract
Abstract Six sets of tetracyanoaurate(III) salts were synthesized and structurally characterized using the metal‐ligand complex cations [RE(bipyO 2 ) 4 ] 3+ (RE = Sc, Y, La; bipyO 2 = 2,2′‐bipyridine‐ N , N ’‐dioxide), [Fe(bipyO 2 ) 3 ] 3+ , [Ln(dmbipyO 2 ) 4 ] 3+ (Ln = Ce, Eu, Yb; dmbipyO 2 = 4,4′‐dimethyl‐2,2′‐bipyridine‐ N , N ’‐dioxide), [Ca(tcmc)] 2+ (tcmc = 1,4,7,10‐tetrakis‐(carbamoylmethyl)‐1,4,7,10‐tetraazacyclododecane), and [Ca(12‐crown‐4) 2 ] 2+ . Noncovalent assembly of the [Au(CN) 4 ] − anions tended to occur via Au···N cyano interactions; however, rare Au(III)···Au(III) contacts between the [Au(CN) 4 ] − groups — suggesting aurophilicity — could be induced when certain cation shape requirements were met. Specifically, cations with shape, size, and symmetry that allowed for packing in a complementary fashion with Au(III)···Au(III) aligned [Au(CN) 4 ] − dimers or trimers — providing efficiently close‐packed layers — were found to be sufficient for manifesting Au(III)···Au(III) contacts. Modifying the [RE(bipyO 2 ) 4 ] 3+ cation with peripheral methyl groups (the [Ln(dmbipyO 2 ) 4 ] 3+ cation) caused isoreticular replacement of a {[Au(CN) 4 ] 3 } 3− trimer with a dumbbell‐shaped {[Au(CN) 4 ] 2 Cl} 3− tri‐anion featuring an unusual Au···Cl···Au bridge — illustrating that the assembly of the anionic groups will adapt to conserve the same close packing. Au(III) aurophilicity between the [Au(CN) 4 ] − groups was studied using computational methods, crystal packing of the structures was probed using Hirshfeld surface analysis, and the emission properties of compounds containing the [Eu(dmbipyO 2 ) 4 ] 3+ luminophore were investigated, showing high quantum yields of ca . 50%.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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".