ChemInform Abstract: THIONE PHOTOCHEMISTRY, THE DETECTION OF A SATURATED THIONE TRIPLET BY LASER FLASH PHOTOLYSIS

Lawrence, A. H.; Mayo, P. De; Bonneau, Roland; Joussot‐Dubien, Jacques

doi:10.1002/chin.197352190

Cited by 4 publications

(22 citation statements)

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“…In this context, we examined the use of cucurbiturils (Scheme 1ii) that are soluble in water under neutral conditions. Cucurbit [7]uril with smaller cavity dimensions formed a better complex than cucurbit [8]uril with the three thioketones examined here. Poor solubility of the CB [8] complex resulted in poor quality NMR spectra.…”

Section: 7mentioning

confidence: 76%

“…Cucurbit [7]uril with smaller cavity dimensions formed a better complex than cucurbit [8]uril with the three thioketones examined here. Poor solubility of the CB [8] complex resulted in poor quality NMR spectra. Therefore, most of our NMR studies were restricted to cucurbit [7]uril.…”

Section: 7mentioning

confidence: 76%

“…The spectra recorded at various host/guest ratios for fenchthione in CB [7] and CB [8] suggest that the emission reaches its maximum with 1.2 equiv of CB [7], whereas in the case of CB [8], a much higher ratio (>6 equiv) is required (Figures 9 and 10). This is consistent with the conclusions drawn from 1 H NMR studies that CB [7] formed a stronger complex than CB [8] with thioketones.…”

Section: 7mentioning

confidence: 99%

“…Phosphorescence spectra of fenchthione, camphorthione, and adamantanethione in water, in the presence of CB [7] and CB [8] are displayed in Figure 8. Since emission studies required a much lower concentration than NMR, we did not face any problem in recording phosphorescence in the presence of CB [8].…”

Section: 7mentioning

confidence: 99%

“…Since emission studies required a much lower concentration than NMR, we did not face any problem in recording phosphorescence in the presence of CB [8].…”

Section: 7mentioning

confidence: 99%

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Closed Nanocontainer Enables Thioketones to Phosphoresce at Room Temperature in Aqueous Solution

et al. 2010

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Thiocarbonyl compounds possess unusual photophysical properties: they fluoresce from S 2 , phosphoresce from T 1 only at extremely low concentrations in solution at room temperature, have unit quantum yield of intersystem crossing from S 1 to T 1 , undergo self-quenching at diffusion-controlled rates, and are quenched by ground-state oxygen leading to self-destruction. In this article, we are concerned with finding a new method to observe phosphorescence from thioketones at room temperature in aqueous solution at high concentrations. To achieve this goal, one needs to find ways to eliminate diffusion-limited self-quenching and oxygen quenching. We present here a general strategy that has allowed us to record phopshorescence from a number of thioketones in aqueous solution at room temperature. The method involves encapsulation of thioketone molecules within a "closed nanocontainer" made up of two cavitand molecules known by its trivial name as octa acid. In these supramolecular complexes, despite two thiocarbonyl compounds being present in close proximity, no self-quenching occurs within the confined space due to curtailment of their rotational freedom. Although phosphorescence could also be observed when these thioketones are included in open containers, such as cucurbiturils and cyclodextrines, the closed container made up of octa acid is found to be the best medium to observe phosphorescence from thioketones whose excited state chemistry is essentially controlled by self-quenching.

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Section: 7mentioning

confidence: 76%

Section: 7mentioning

confidence: 76%

Section: 7mentioning

confidence: 99%

Section: 7mentioning

confidence: 99%

“…Since emission studies required a much lower concentration than NMR, we did not face any problem in recording phosphorescence in the presence of CB [8].…”

Section: 7mentioning

confidence: 99%

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