Silver Coodination Polymers with Flexible Ligands. Syntheses, Crystal Structures, and Effect of the Counteranion and the Solvent on the Structure of Complexes [Ag<b>L</b>X]<sub>∞</sub> of the Bis(Phenylthio)methane Ligand <b>L</b><b><sup>1</sup></b> with Silver(I) Salts, X = ClO<sub>4</sub><sup>-</sup>, BF<sub>4</sub><sup>-</sup>, CF<sub>3</sub>COO<sup>-</sup>, CF<sub>3</sub>SO<sub>3</sub><sup>-</sup>, CF<sub>3</sub>CF<sub>2</sub>CF<sub>2</sub>COO<sup>-</sup>, and <sup>-</sup>OOCCF<sub>2</sub>CF<sub>2</sub>COO<sup>-</sup>
Bibliographic record
Abstract
A number of complexes were synthesized to rationalize the structures of Ag(I) complexes with a small flexible bidentate ligand, bis(phenylthio)methane, when the anion is varied. We compared two similar “spherical” anions, ClO 4 - ( 1 ) and BF 4 - ( 2 ), as well as two slightly “elongated” ones, CF 3 COO - ( 3 ) and CF 3 SO 3 - ( 4, 5 ). Complexes with a longer anion, CF 3 CF 2 CF 2 COO - ( 6 ), and a diacid, - OOCCF 2 CF 2 COO - ( 7 ), were also investigated. All the compounds studied form a 1D-coordination polymer. The coordination polymers of 1 − 4 are of the type [Ag−ligand−] ∞ and adopt two distinct conformations: gauche−trans−gauche for 1, 2, and 4, and gauche−gauche−gauche for 3 . The anions in 1 − 4 are coordinated to the silver atoms through a single O or F atom. All these 1D-chains are associated through weak van der Waals interactions into 2D-layer structures. Solvent-induced supramolecular isomerism was observed with the CF 3 SO 3 - anion. With diethyl ether, the 1D-coordination polymer of 4 was observed, as indicated above, while a two-stranded chain comprising a 16-membered macrocyclic structure, Ag 4 L 1 4, was noted when petroleum ether was used, 5 . The macrocycles are connected through a small cyclic (CF 3 SO 3 ···Ag···) 2 dimeric unit. Another type of double-stranded ladder-like structure was noted for 6 . Each of the two heptafluorobutyrate anions is coordinated through its oxygen atoms to two distinct silver atoms to form a dimeric unit. This, in turn, is connected to another unit through two Ag−S coordination bonds. The repeat unit of this coordination polymer is based on a 10-membered Ag 4 L 1 2 macrocycle. In compound 7, with the tetrafluorosuccinate anion, one observes another type of 1D-polymer best described as a [Ag 2 −tetrafluorosuccinate−] ∞ chain reinforced by Ag−ligand−Ag bonds. Most complexes containing fluorine atoms have C(H)···F or C(H 2 )···F short contacts (2.998−3.203 Å) that correlate with an FTIR absorption band around 521 cm -1 . Relatively short Ag···Ag interactions are found in both 6 and 7 .
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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".