Photo‐Induced Assembly of a Luminescent Tetraruthenium Square
Bibliographic record
Abstract
Abstract Self‐assembly is a powerful synthetic tool that has led to the development of one‐, two‐ and three‐dimensional architectures. From MOFs to molecular flasks, self‐assembled materials have proven to be of great interest to the scientific community. Here we describe a strategy for the construction and de‐construction of a supramolecular structure through unprecedented photo‐induced assembly and dis‐assembly. The combination of two approaches, a [n×1]‐directional bonding strategy and a ligand photo‐dissociation strategy, allows the photo‐induced assembly of a polypyridyl RuII precursor into a discrete molecular square. Diffusion‐ordered NMR spectroscopy confirmed the synthesis of a higher volume species, while the identity of the species was established by high‐resolution mass spectrometry and single‐crystal X‐ray diffraction studies. The self‐assembled square is not obtained by classical thermal techniques in similar conditions, but is obtained only by light‐irradiation. The tetraruthenium square has an excited‐state lifetime (135 ns), 40 times that of its mononuclear precursor and its luminescence quantum yield (1.0 %) is three orders of magnitude higher. These remarkable luminescence properties are closely related to the relatively rigid square structure of the tetraruthenium assembly, as suggested by slow radiationless decay and transient absorption spectroscopy. The results described herein are a rare example of photo‐induced assembly and dis‐assembly processes, and can open the way to a new avenue in supramolecular chemistry, leading to the preparation of structurally organized supermolecules by photochemical techniques.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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) | 0.002 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), 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".