Tuning the Structures of Mercury Cyanide-Based Coordination Polymers with Transition Metal Cations
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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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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 | 0.000 | 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 it