Photochemistry of Ketones in Carbon Tetrachloride Solution

1973 ◽  
Vol 51 (9) ◽  
pp. 1435-1440 ◽  
Author(s):  
J. O. Pavlik ◽  
P. I. Plooard ◽  
A. C. Somersall ◽  
J. E. Guillet
Keyword(s):  
Energy Transfer ◽  
Carbon Tetrachloride ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Definitive Evidence ◽  
Carbon Tetrachloride Solution ◽  
Radiationless Energy Transfer ◽  
Norrish Type ◽  
Low Efficiency

Acetone, chloroacetone, 4-heptanone, 8-pentadecanone, 12-tricosanone, and dimethyl γ-keto pimellate were photolyzed at 3130 Å in carbon tetrachloride solution. The quantum yields of C2Cl6 formed, the decrease in Norrish type I and type II products, the copious yields of HCl and the Stern–Volmer quenching of ketone fluorescence by carbon tetrachloride provide definitive evidence for energy transfer which is rationalized by an exciplex mechanism of low efficiency. The excited [n,π*]1 state of the ketone forms a loose complex with the CCl4 and radiationless energy transfer leads to dissociation of the CCl4 in the primary chemical step.

scholarly journals Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type ◽  
Migration Pathways

The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.<br>

scholarly journals Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type ◽  
Migration Pathways

The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.<br>

scholarly journals Competition between cyclization and unusual Norrish type I and type II nitro-acyl migration pathways in the photouncaging of 1-acyl-7-nitroindoline revealed by computations

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Migration Pathway ◽  
Norrish Type ◽  
Triplet Excited States ◽  
Migration Pathways

AbstractThe 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and an acyl migration pathway, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish type I and a 1,6-nitro-acyl variation of a Norrish type II mechanism, which is reported here for the first time. We also found negligible energetic differences in the uncaging mechanisms of the 4-methoxy-5,7-dinitroindolinyl (MDNI) cages and their mononitro analogues (MNI). We traced the experimentally observed improved quantum yields of MDNI to a higher population of the reactants in the triplet surface. This fact is supported by a more favorable intersystem crossing due to the availability of a higher number of triplet excited states with the correct symmetry in MDNI than in MNI. Our findings may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.

scholarly journals Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type ◽  
Migration Pathways

The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.<br>

scholarly journals Unusual Norrish Type I and Type II Nitro-Acyl Migration Transition State in the Photo-Uncaging of 1-Acyl-7-Nitroindolines Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Transition State ◽  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type

The 7-nitroindolinyl family of caging chromophores has received a lot of attention in the past two decades. However, it is not clear if they undergo cyclization or migration upon photo-uncaging to release the active compound. In this study, we performed state-of-the-art density functional theory calculations to fully understand the photo-uncaging mechanism and we compared the probabilities of all plausible pathways. We found that the key transition state in the lowest¬ energy pathway involves an acyl migration. It possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which has not been previously reported. We also introduced a new computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and more efficient agonist release.<br><br>

scholarly journals Surface plasmon enhanced energy transfer between type I CdSe/ZnS and type II CdSe/ZnTe quantum dots

2010 ◽  
Vol 96 (7) ◽  
pp. 071906 ◽  
Author(s):  
C. H. Wang ◽  
C. W. Chen ◽  
Y. T. Chen ◽  
C. M. Wei ◽  
Y. F. Chen ◽  
...  
Keyword(s):  
Quantum Dots ◽  
Energy Transfer ◽  
Surface Plasmon ◽  
Type I ◽  
Type Ii

Intrazeolite photochemistry. II. Evidence for site inhomogeneity from studies of aromatic ketone phosphorescence

1985 ◽  
Vol 63 (6) ◽  
pp. 1308-1314 ◽  
Author(s):  
H. L. Casal ◽  
J. C. Scaiano
Keyword(s):  
Energy Transfer ◽  
Luminescent Properties ◽  
Cooperative Effect ◽  
Type Ii ◽  
Oxygen Quenching ◽  
Aromatic Ketones ◽  
Transfer Processes ◽  
Norrish Type ◽  
Triplet Lifetime ◽  
Conformational Restrictions

The luminescent properties of several aromatic ketones included in the hydrophobic zeolite Silicalite have been examined. Acetophenone, benzophenone, and β-phenylpropiophenone show readily detectable phosphorescence; by contrast, valerophenone does not luminesce, but undergoes the Norrish Type II reaction. Thus, irradiated samples of valerophenone in Silicalite show phosphorescence due to the accumulation of acetophenone. In the case of β-phenylpropiophenone the triplet lifetime is ca. 100 000 times longer than the solution value, suggesting severe conformational restrictions. Co-inclusion of acetophenone with various substrates and oxygen quenching studies indicate that Silicalite has at least two distinct classes of inclusion sites. In one of them energy transfer processes are rapid and efficient, suggesting a cooperative effect in the inclusion of ketones in these regions of the Silicalite framework.

scholarly journals Structural Causes of Singlet/triplet Preferences of Norrish Type II Reactions in Carbonyls

2020 ◽  
Author(s):  
Keiran Rowell ◽  
Scott Kable ◽  
Meredith J. T. Jordan
Keyword(s):  
Hydrogen Abstraction ◽  
Conical Intersection ◽  
Quantum Yields ◽  
Type Ii ◽  
Structure Activity ◽  
Abstraction Reaction ◽  
Norrish Type ◽  
Close Proximity ◽  
Unsaturated Carbonyls ◽  
Hydrogen Abstraction Reaction

Photolysis thresholds are calculated for the Norrish Type II (NTII) intramolecular γ-hydrogen abstraction reaction in 22 structurally informative carbonyl species. The B2GP-PLYP excited state <i>S</i><sub>1</sub> and <i>T</i><sub>1</sub> thresholds agree well with triplet quenching experiments. However, many linear-response methods deliver poor <i>S</i><sub>1</sub> energetics, which is explained by a <i>S</i><sub>1</sub>/<i>S</i><sub>0</sub> conical intersection in close proximity to the <i>S</i><sub>1 </sub>transition state. Multiconfigurational CASSCF calculations confirm a conical intersection features across all carbonyl classes. <div><br></div><div>Structure–activity relationships are determined that could be used in atmospheric carbonyl photochemsitry modelling. This is exemplified for butanal, whose NTII quantum yields are too low when used as a ‘surrogate’ for larger carbonyls, since butanal lacks the γ-substitution that stabilises the 1,4- biradical. Reaction on <i>T</i><sub>1</sub> dominates only in species where the <i>S</i><sub>1</sub> thresholds are high — typically ketones. The α, β-unsaturated carbonyls cannot cleave the α–β bond, causing them to photoisomerise. A concerted <i>S</i><sub>0</sub> NTII mechanism is calculated to be viable and may explain the recent detection of NTII photoproducts in the photolysis of pentan-2-one below the <i>T</i><sub>1</sub> threshold.</div>

scholarly journals Structural Causes of Singlet/triplet Preferences of Norrish Type II Reactions in Carbonyls

2020 ◽  
Author(s):  
Keiran Rowell ◽  
Scott Kable ◽  
Meredith J. T. Jordan
Keyword(s):  
Hydrogen Abstraction ◽  
Conical Intersection ◽  
Quantum Yields ◽  
Type Ii ◽  
Structure Activity ◽  
Abstraction Reaction ◽  
Norrish Type ◽  
Close Proximity ◽  
Unsaturated Carbonyls ◽  
Hydrogen Abstraction Reaction

Photolysis thresholds are calculated for the Norrish Type II (NTII) intramolecular γ-hydrogen abstraction reaction in 22 structurally informative carbonyl species. The B2GP-PLYP excited state <i>S</i><sub>1</sub> and <i>T</i><sub>1</sub> thresholds agree well with triplet quenching experiments. However, many linear-response methods deliver poor <i>S</i><sub>1</sub> energetics, which is explained by a <i>S</i><sub>1</sub>/<i>S</i><sub>0</sub> conical intersection in close proximity to the <i>S</i><sub>1 </sub>transition state. Multiconfigurational CASSCF calculations confirm a conical intersection features across all carbonyl classes. <div><br></div><div>Structure–activity relationships are determined that could be used in atmospheric carbonyl photochemsitry modelling. This is exemplified for butanal, whose NTII quantum yields are too low when used as a ‘surrogate’ for larger carbonyls, since butanal lacks the γ-substitution that stabilises the 1,4- biradical. Reaction on <i>T</i><sub>1</sub> dominates only in species where the <i>S</i><sub>1</sub> thresholds are high — typically ketones. The α, β-unsaturated carbonyls cannot cleave the α–β bond, causing them to photoisomerise. A concerted <i>S</i><sub>0</sub> NTII mechanism is calculated to be viable and may explain the recent detection of NTII photoproducts in the photolysis of pentan-2-one below the <i>T</i><sub>1</sub> threshold.</div>

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