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 distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.003 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| 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 teacher head, 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".