Applications of Photogenerated “Dark Isomer” Boriranes: Dearomatization and Thermal Energy Storage
Bibliographic record
Abstract
The works described herein investigate the bimolecular ground state reactivity of boron-containing photochromic systems. Despite a remarkable development in the synthesis and characterization of N,C- and C,C-chelate organoboron species over the last decade, only their photoreactivity and photophysical properties have been well documented. Their ground state reactivity is largely unknown, and apart from luminescence, no applications exploiting their photochromic properties have been reported. To complement their photoreactive profiles, N,C- and C,C-chelate organoboron species will be reacted with conventional organic reagents to target specifically the boron center and boron-chelated ligands to elucidate structural changes in thermal conditions. The first study describes the one-pot, light-assisted dearomative functionalization of N,C and C,C-chelate four-coordinate boron compounds via [4+2] cycloaddition (Diels-Alder reaction) at a boron-anchored mesityl ring. The synthesis progressed rapidly under ambient conditions and all of the four products reported in this work contain a borirane ring that is stable towards oxygen, unlike its starting precursors which undergo oxidative deborylation. The simplicity of this post synthetic modification strategy prompts further investigation into boron-assisted dearomatization of simple aromatic rings. The second study uses a N,C-chelate four coordinate boron photoswitch for solar energy storage. The compound of interest photoisomerizes from a four-coordinate organoboron to a borirane-containing species with 365 nm light and was found to liberate 14 kcal/mol of energy upon its thermally triggered reversion back to the original organoboron in the solid state. We find that the reverse reaction from borirane to N,C-chelate boron compound can be catalyzed by three salts containing the −B(C6F5) counter ion. Radical species were discovered as key intermediates in the reversal process and were detected via NMR and EPR spectroscopy. The facile reversal of the photoswitch and detection of heat generated in the reversal process make this class of compounds suitable candidates for solar energy storage applications.
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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) | 0.003 | 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 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".