Chelates of β-Diketones. I. Enolization, Ionization and Spectra

Hammond, George S.; Borduin, Wilfred G.; Guter, Gerald A.

doi:10.1021/ja01526a058

Cited by 67 publications

(22 citation statements)

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“…All predicted rate constants were capped at the diffusion controlled limit of 10 10 M −1 s −1 . Complete extinction coefficients across all actinic wavelengths were not available for most compounds, but published values of λ max and ε max are available for many carbonyl compounds (Xu et al, 1993;Malik and Joens, 2000;Steenken et al, 1975;Hammond et al, 1959;Mackinney and Temmer, 1948;Schutze and Herrmann, 2004;Rice, 1920;Gubina et al, 2004). For simple mono-and di-carbonyl compounds without published λ max and ε max values (76 out of 92 total compounds), we made educated upper estimates based on the values of compounds with similar functionality.…”

Section: Role Of Photolysis In Aqueous Processing Of Carbonylsmentioning

confidence: 99%

Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

Epstein¹,

Tapavicza²,

Furche³

et al. 2013

Preprint

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Gas phase photolysis is an important tropospheric sink for many carbonyl compounds, however the significance of direct photolysis of carbonyl compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived Henry's law parameters, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations of atmospherically relevant carbonyl compounds designed to estimate gas and aqueous phase extinction coefficients. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only three out of the 92 carbonyl compounds investigated, pyruvic acid, 3-oxobutanoic acid, and 3-oxopropanoic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α, β conjugation, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected

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Section: Role Of Photolysis In Aqueous Processing Of Carbonylsmentioning

confidence: 99%

Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

Epstein¹,

Tapavicza²,

Furche³

et al. 2013

Preprint

View full text Add to dashboard Cite

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“…The amount of enol form decreases with increasing temperatures. As the degree of enolization increases, the acidity of the enol proton decreases (Hammond et al, 1959). In the case of unsymmetrically-substituted β-diketones, two different enol forms are possible.…”

Section: Overview Of β-Diketone Ligands and Types Of Complexesmentioning

confidence: 99%

“…The authors argue that lower yields of synthesis in air are caused by destructive air oxidation. Air oxidation during synthesis has been observed for transition metal β-diketonates as well, for instance for [Ni(thd) 2 ] (Johnson and Hammond, 1959).…”

Section: Synthetic Strategiesmentioning

confidence: 99%

Rare-earth beta-diketonates

Binnemans

2005

Handbook on the Physics and Chemistry of Rare Earths

398

303

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Contents 157 5.6. Solution structure 157 5.7. Electrochemical properties 158 5.8. Thermodynamic properties 159 5.9. Magnetic properties 159 5.10. Crystal-field splittings 160 5.11. Infrared spectra 161 5.12. Chirality sensing 161 5.13. Properties of hemicyanine dyes with βdiketonate counter ions 162 6. Luminescence of β-diketonate complexes 162 6.1. Photoluminescence 162 6.2. Electroluminescence 178 6.3. Triboluminescence 179 6.4. Sensitized chemiluminescence 183 7. From complexes to materials 185 7.1. Sol-gel glasses 185 7.2. Ormosils 186 7.3. β-Diketonates in polymer matrices 190 7.4. β-Diketonates in zeolites 195 7.5. Langmuir-Blodgett films (LB films) 197 7.6. Liquid crystals 200 7.7. Nonlinear optical materials 203 8. From materials to devices 205 8.1. Chelates for lasers 205 8.2. Organic light-emitting diodes (OLEDs) 206 8.3. Liquid crystal displays (LCDs) 216 8.4. Polymeric optical waveguides and amplifiers 217 9. NMR shift reagents 218 9.1. Historical development and general principles 218 9.2. Achiral shift reagents 221 9.3. Chiral shift reagents 226 10. Analytical applications 227 10.1. Trace analysis of lanthanide ions 227 10.2. Trace analysis of organic and biomolecular compounds 229 10.3. Luminescent visualization of latent fingerprints 230 10.4. Chemical sensors 232 10.5. Stationary phases in gas chromatography 232 11. Applications of volatile complexes 233 11.1. Volatile β-diketonate complexes 233 11.2. Gas chromatographic separation of the rare earths 237 11.3. Preparation of thin films by metalorganic chemical vapor deposition (MOCVD) 238 11.4. Preparation of thin films by atomic layer deposition (ALD) 241 11.5. Fuel additives 242 12. Solvent extraction 243 13. Catalytic properties 247

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“…As can be seen in Figure 4a, the copolymer 1-50 has an intense absorption maximum at 362 nm, which is attributed to the p-p* transitions of the enols. 17 The absorption peak at 379 nm, which is attributed to the p-p* electron transition from dibenzoylmethane, is Blue emission from polymer nanocomposites T Otsuka and Y Chujo slightly red-shifted for the copolymer 1-50/ZrO 2 -NC composite from that of the copolymer 1-50. Furthermore, the spectra for the co polymer 1-50/ZrO 2 -NC composite show that the new shoulder peak B410 nm, which arises from the zirconium 1,3-diketonate complex, is similar to the absorption maximum of boron 1,3-diketonate dyes from the design of diarylboron complexes.…”

Section: Morphology Of Mdbm-containing Copolymer/zro 2 -Nc Compositesmentioning

confidence: 98%

Blue emission from polymer nanocomposites: preparation and application of multicolored luminescent materials

Ôtsuka

Chujo

2011

Polym J

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Blue-emitting luminescent polymer nanocomposites were prepared from 1,3-diketone functionalized poly(methyl methacrylate) (PMMA) and zirconium oxide nanocrystals (ZrO 2 -NCs). Fourier transform infrared spectra suggested chemisorption of the 1,3-diketone by bidentate chelation of the diketonate anion to the ZrO 2 -NC surface. The ZrO 2 -NCs were well dispersed in the polymer matrix and crosslinked on the NC surfaces. The chemically crosslinked polymer nanocomposites had high photostability compared with the PMMA/ZrO 2 -NC composites with 1,3-bis(4-methoxyphenyl)-1,3-propanedione. The stability of the luminescence from the polymer nanocomposites was enhanced because the 1,3-diketonate binding sites were fixed between inorganic NCs and polymer chains. The blue emission peaking at 448 nm can be tuned by the addition of 8-hydroxyquinolinecontaining copolymer/ZrO 2 -NC composite, which red-shifted the emission from blue to yellow and green as a function of the blend composition. This strategy, in which the ligand would be immobilized by an organic/inorganic sandwich structure, is suitable for obtaining not only well-stabilized luminescent nanocomposites but also nano-optoelectronics with controlled emission colors.

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Chelates of β-Diketones. I. Enolization, Ionization and Spectra

Cited by 67 publications

References 0 publications

Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

Rare-earth beta-diketonates

Blue emission from polymer nanocomposites: preparation and application of multicolored luminescent materials

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