Polymerization of Self-Assembled Tetraazaporphyrins
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Bibliographic record
Abstract
Polymerization of self-assembled supramolecular structures considerably increases their often limiting thermal and chemical stability, which widens their potential application in commercial products. Particularly interesting for self-assembled materials is the topochemical polymerization of diacetylenes to polydiacetylenes because it can be initiated photochemically and thermally without the need for additives, it proceeds with minimal structural changes, and it generates new functionality since polydiacetylene is a 1-dimensional organic semiconductor and absorbs visible light. Polydiacetylenes have been generated in single crystals, gel phases, thin films, and membranes but their formation in mesophases, such as liquid crystals, has been surprisingly little studied although higher ordered mesophases should support the topochemical polymerization of diacetylenes (1,3-butadiyne groups) and may give access to large domains of uniformly aligned materials. Presented here are tetraazaporphyrins that contain eight alkyl chains with diacetylene groups to probe their mesomorphism and conversion into multifunctional polydiacetylene materials. While incorporation of diacetylene groups supports columnar mesomorphism, successful photopolymerization required the presence of directing amide groups that suppressed columnar in favour of nematic mesomorphism. Still, polymerization of the nematic mesophase generated a soluble nematic polydiacetylene of significantly higher molecular weight (Mn = 77 kDa or 25 monomer units by GPC) than what has been obtained in gel phases of related compounds. Formation of polydiacetylene was confirmed by Raman spectroscopy and its nematic structure was verified by UV-vis spectroscopy, polarized optical microscopy, and X-ray diffraction. Both, its nematic structure and the incorporation of eight side-chains per discotic unit provide the polydiacetylene with sufficient solubility for casting thin films on substrates. AFM studies of films casted onto silicon wafers revealed a grid-like structure of connected nanofibers.
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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) | 0.000 | 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