Intra- and Intermolecular Second-Sphere Coordination Chemistry: Formation of Capsules, Half-Capsules, and Extended Structures with Hexaaquo- and Hexaamminemetal Ions
Why this work is in the frame
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Bibliographic record
Abstract
In the design of novel extended solids, particularly those based on weaker interactions, reliable "synthons" are a valuable commodity. This work concerns the hydrogen-bonded assemblies which result from the second-sphere coordination interactions between a highly preorganized trisulfonate ligand and hexaaquo metal ions. Significantly, supramolecular structural variation, which may be rationalized on the basis of the features of the molecular building blocks, is observed. The results are formation of second-sphere capsules with trivalent ions (Fe(3+), Cr(3+), Al(3+)), and half-capsules with divalent ions (Mg(2+), Zn(2+)). The divalent systems further assemble into extensively hydrogen-bonded hexagonal nets. Effects of geometrical variation of the building blocks are also observed when a Jahn-Teller-distorted divalent ion (Cu(2+)) is substituted for the perfectly octahedral species. The second-sphere effects on the stabilization of the primary coordination sphere are illustrated by TGA experiments. In these assemblies, the potential of a new supramolecular synthon is illustrated, that being the complementary cis-aquo sulfonate interaction. These complexes illustrate the general utility of second-sphere effects, both as an assembly tool and to stabilize metal complexes in the solid state. Finally, as a comparison, a hydrogen-bonded assembly with a hexaammine complex of a trivalent metal (Co(3+)) is presented, which forms an extended network with a completely altered hydrogen bonding array.
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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) | 0.005 | 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