Heteroleptic Cu-Based Sensitizers in Photoredox Catalysis
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Bibliographic record
Abstract
Photochemistry is an important tool in organic synthesis that has largely been underdeveloped in comparison to thermal activation. Recent advances in technology have ushered in a new era in synthetic photochemistry. The emergence of photocatalysis, which exploits sensitizers for the absorption of visible light, has provided organic chemists with a new route to the generation of radical intermediates for synthesis. Of particular interest is the development of Cu-based complexes for photocatalysis, which possess variable photophysical properties and can display complementary reactivity with common photocatalysts based on heavier transition metals such as Ru or Ir. Heteroleptic Cu-based sensitizers incorporating the presence of both a bisphosphine and diamine ligand bound to the copper center are a promising class of photocatalysts. Their synthesis is a single step, often involving only precipitation for purification. In addition, it was shown that the sensitizers could be formed in situ in the reaction mixture, simplifying the experimental setup. The heteroleptic nature of the Cu-complexes also affords opportunities to fine-tune properties. For example, structurally rigidified bisphosphines reinforce geometries about the metal center to extend the excited state lifetime. Variation of the diamine ligand can influence the excited state oxidation/reduction potentials and optical absorbances. The heteroleptic complex Cu(XantPhos)(neo)BF4 has demonstrated utility in the synthesis of helical polyaromatic carbocycles. The synthesis of [5]helicene, a relatively simple member of the helicene family, was improved from the existing UV-light mediated method by eliminating the formation of unwanted byproducts. In addition, the Cu-based sensitizers also promoted the formation of novel pyrene/helicene hybrids for materials science applications. The synthetic methods that were developed were augmented when combined with continuous flow technology. The irradiation of reaction mixtures as they are pumped through small diameter tubing provides a more homogeneous and increased photon flux compared with irradiation in round-bottom flasks or other batch reactors. The value of continuous flow methods is also evident when examining UV-light photochemistry, where the simple and safe experimental set-ups allow for further exploration of high energy light for synthetic purposes. The synthesis of functionalized complex carbazoles was also studied using both a visible light method exploiting a heteroleptic copper-based sensitizer and a UV-light mediated method. It was demonstrated that both the photocatalysis methods and UV light photochemistries were rendered more user-friendly, safe, and reproducible when using continuous flow methods. Interestingly, the two photochemical methods often afford contrasting selectivities as a result of their inherently different mechanisms. It can be expected that the complementarity of the various photochemical methods will be an asset to synthetic chemists as the field continues to evolve.
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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 | 0.001 | 0.005 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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