Modified Metal Dibenzoylmethanates for Soft Supramolecular Materials: Extension to Oligomeric and Polymeric Host Receptors with Nanosized Void Spaces
Bibliographic record
Abstract
Recently reported molecular host complexes, modified metal dibenzoylmethanates (metal DBMs), are extended to polynuclear host receptors by connecting metal DBM units with bridging ligand 4,4‘-dipyridyl (bipy). Series of new solvent-free as well as inclusion materials were prepared and studied with XRD, NMR, and other methods. Template-directed synthesis gave inclusion compounds with three distinct types of host receptors: dimeric [Zn 2 (bipy)(DBM) 4 ], trimeric [Zn 3 (bipy) 2 (DBM) 6 ], and polymeric [Zn(bipy)(DBM) 2 ] n complexes. The dimeric complex was isolated as a solvent-free compound and as inclusion compounds with tert -butylbenzene and fluorobenzene (host per guest molar ratios of 1:1 and 1: 2 / 3, respectively). The trimeric complex was prepared as an inclusion compound with DMSO (1:5 molar ratio). The polymeric complex was observed in inclusion compounds with fluorobenzene (host unit per guest molar ratio 1:2), tetrahydrofuran (1:2), 2-pentanone (1:2), bipy/DMSO (1: 1 / 2: 1 / 2 ), and bipy/ tert -butylbenzene (1:1:2); a solvent-free material was obtained upon desolvation of tetrahydrofuran and 2-pentanone inclusions. The isolated host species have five-coordinated terminal zinc centers (two chelating DBMs and a singly coordinating bipy) and octahedrally coordinated intrinsic zinc centers (two chelating equatorial DBMs and two singly coordinating bipys). The bipy ligands bridge the zinc centers to give the di-, tri-, and polynuclear complexes. Nanosized voids between the DBM units coordinated to adjacent zinc centers form the basis for cages and channels in the inclusion materials. These voids have, in many cases, a typical size of between 1 and 2 nm and accommodate up to five molecules per single cavity or two rows of guest molecules in a single channel. When compared to previously reported metal DBMs, the multinuclear metal DBM receptors reported here exhibit stronger inclusion affinity and enhanced inclusion capacity.
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How this classification was reachedexpand
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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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 teacher head, 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".