Tuning the Structures of Mercury Cyanide-Based Coordination Polymers with Transition Metal Cations
Bibliographic record
Abstract
A series of complexes containing [ML x ]Cl 2 (M = Mn, Cu, Ni; L = 2,2‘-bipyridine (bipy), 1,10-phenanthroline (phen), 2,2‘:6‘,6‘ ‘-terpyridine (terpy), diethylenetriamine (dien), tris(2-aminoethyl)amine (tren); x = 1 or 2) and linear, neutral Hg(CN) 2 building blocks have been synthesized and structurally characterized. In general, the Lewis acidic Hg(CN) 2 moieties accept chloride ligands from the M(II) centers, in several cases increasing the structural dimensionality of the system as a result. [ML 2 (μ-Cl) 2 Hg(CN) 2 ] (M = Mn, Ni; L = bipy, phen) ( 1 − 4 ) are molecular complexes in which the chloride ligands bridge the M(II) and mercury(II) centers; π···π stacking between the aromatic rings from different molecules increases the structural dimensionality. [Cu(terpy)Cl 2 (μ-Hg(CN) 2 )] ( 5 ) is an alternating 1-D chain of Cu(terpy)Cl 2 and Hg(CN) 2 moieties in which the chloride ligands bridge to different mercury(II) centers. When two phen ligands are used with copper(II), an additional Hg(CN) 2 unit is incorporated to form {[Cu(phen) 2 Cl] 2 Hg(CN) 2 [Hg(CN) 2 Cl] 2 } ( 6 ), an alternating 1-D chain of [Hg(CN) 2 Cl] 2 2- dimers that are N-bound to Hg(CN) 2 units that also bind to dangling [Cu(phen) 2 Cl] + moieties. In [Cu(dien)Cl][Hg(CN) 2 Cl] ( 7 ), 1-D chloride bridged [Hg(CN) 2 Cl] n n - double salt chains formed in situ during polymer formation are held in place by chloride bridged [Cu(dien)Cl] 2 2+ cationic dimers to form a 2-D brick-wall layer motif. Two 1-D double salt chains, one cationic and one anionic, which hydrogen bond together to form neutral columns are generated in [Cu(tren)Hg(CN) 2 Cl][HgX 2 Cl] ( 8 ). N-cyano coordination and chloride bridging from Hg(CN) 2 and chloride ligands in {[Ni(tren)] 4 [Hg(CN) 2 ] 8 Cl 6 }HgCl 4 ( 9 ) generate 1-D cationic columns of {[Ni(tren)] 4 [Hg(CN) 2 ] 8 Cl 6 } n 2 n + which hydrogen bond to tetrahedral [HgCl 4 ] 2- moieties, increasing the structural dimensionality of this noncentrosymmetric complex. Factors influencing the structural dimensionality and the induction of N-cyano bridging are discussed.
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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 | 0.000 |
| 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".