Self-Assembly of Polymer and Sheet Structures from Palladium(II) Complexes by Hydrogen Bonding between Carboxamide Substituents
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Bibliographic record
Abstract
The self-assembly of supramolecular structures from either neutral or cationic palladium(II) complexes containing primary or secondary carboxamide groups as substituents on pyridine ligands has been explored. The displacement of PhCN in trans-[PdCl(2)(PhCN)(2)] by L = N-methylnicotinamide (MNA), isonicotinamide (INA), or nicotinamide (NA) gave the corresponding complexes trans-[PdCl(2)L(2)] 1-3, respectively. Complex 1.H(2)O forms a 2D sheet network via amide-amide hydrogen bonding supported by chloride ligand-to-water hydrogen-bonding interactions. Several cationic complexes, [Pd(L'L')L(2)](2+) 4-9 and 11-16, containing the above ligands and with PPh(3), dppp, dppm, or bu(2)bipy as ancillary ligand(s) were prepared. Complex 4 (L = MNA, L'L' = dppp) forms dimers through amide-amide hydrogen bonding, forming macrocycles which further propagate to form chains via weak C-H...O=C hydrogen bonding. Complex 6 (L = NA, L'L' = dppp) forms zigzag chains connected by amide head-to-head hydrogen bonds. Complex 8 (L = INA, L'L' = dppm) gives interesting double-stranded ribbons linked by two types of amide--amide hydrogen-bonding interactions. Complex 13 (L' = PPh(3), L = NA) forms an infinite chain via complementary amide-amide hydrogen bonds. Complex 14 (L = MNA, L'L' = bu(2)bipy) forms infinite ribbons via the combination of amide hydrogen bonding mediated by a BF(4) anion and weak C-H...O=C hydrogen bonding. Complex 15 (L = INA, L'L' = bu(2)bipy) gives a ladder polymer formed through amide--amide hydrogen bonds. The structure of cis-[Pd(PPh(3))(2)(OH(2))(2)] (OTf)(2) (10) is also reported.
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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 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.002 | 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 it