Efficient intersystem crossing using singly halogenated carbomethoxyphenyl porphyrins measured using delayed fluorescence, chemical quenching, and singlet oxygen emission

2015 ◽  
Vol 17 (43) ◽  
pp. 29090-29096 ◽  
Author(s):  
Dawn M. Marin ◽  
Sonia Payerpaj ◽  
Graham S. Collier ◽  
Angy L. Ortiz ◽  
Gaurav Singh ◽  
...  
Keyword(s):  
Excited State ◽  
Singlet Oxygen ◽  
State Formation ◽  
Delayed Fluorescence ◽  
Intersystem Crossing ◽  
Fluorescence Lifetimes ◽  
Triplet Excited State

Singly halogenated carbomethoxyphenylporphyrins show decreased singlet fluorescence lifetimes and increased rates of triplet excited state formation.

The mechanism of the photochemical cycloaddition reaction of N-benzoylindole with cyclopentene

1990 ◽  
Vol 68 (10) ◽  
pp. 1685-1692 ◽  
Author(s):  
Bimsara W. Disanayaka ◽  
Alan C. Weedon
Keyword(s):  
Excited State ◽  
Quantum Yield ◽  
Ground State ◽  
Mechanistic Model ◽  
Cycloaddition Reaction ◽  
Intersystem Crossing ◽  
Triplet Excited State ◽  
Excited State Lifetime ◽  
Yield Data ◽  
Counting Procedure

The mechanism of the photochemical cycloaddition reaction between N-benzoylindole, 1, and cyclopentene to give cyclobutane adducts 2 and 3 has been examined. The triplet excited state lifetime and quantum yield of intersystem crossing were determined for 1 as (2.8 ± 0.3) × 10−8 s and 0.39 ± 0.01, respectively, using the triplet counting procedure. In addition, the dependence of the quantum yield of cycloadduct formation upon the concentration of cyclopentene and upon the concentration of excited state quenchers has been determined. The results are used to propose a mechanistic model in which the triplet excited state of 1 reacts with cyclopentene to give a triplet 1,4-biradical intermediate. Following spin inversion the biradical intermediate reverts to the ground state starting materials or proceeds to the products 2 and 3; this partitioning, along with the quantum yield of intersystem crossing, gives rise to a limiting quantum yield of cycloaddition at infinite alkene concentration of 0.061. It is calculated that 84% of the biradical intermediates revert to the starting materials and 16% proceed to cycloadducts. The quantum yield data are also used to calculate two independent values of the rate constant for reaction of the triplet excited 1 with alkene; the values are (1.8 ± 0.1) × 107M−1 s−1 and (4.0 ± 0.8) × 106 M−1 s−1'. Some evidence for self quenching of the triplet excited state of 1 by ground state 1 was also observed. The quantum yield of intersystem crossing and the triplet excited state lifetime of 1 were found to vary with the solvent used; this is discussed in terms of the possible existence of a charge transfer triplet excited state. Keywords: indole, photocycloaddition, mechanism.

scholarly journals Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

2016 ◽  
Vol 7 (6) ◽  
pp. 3621-3631 ◽  
Author(s):  
Seda Cekli ◽  
Russell W. Winkel ◽  
Erkki Alarousu ◽  
Omar F. Mohammed ◽  
Kirk S. Schanze
Keyword(s):  
Excited State ◽  
Intersystem Crossing ◽  
Triplet Excited State ◽  
Acceptor Interaction ◽  
Donor Acceptor

Intersystem crossing in π-conjugated donor–acceptor–donor chromophores is controlled by the strength of the donor–acceptor interaction.

Morphology dependence of the triplet excited state formation and absorption in polyfluorene

2005 ◽  
Vol 71 (24) ◽  
Author(s):  
Anna Hayer ◽  
Amena L. T. Khan ◽  
Richard H. Friend ◽  
Anna Köhler
Keyword(s):  
Excited State ◽  
State Formation ◽  
Triplet Excited State

scholarly journals Control of triplet state generation in heavy atom-free BODIPY–anthracene dyads by media polarity and structural factors

2018 ◽  
Vol 20 (12) ◽  
pp. 8016-8031 ◽  
Author(s):  
Mikhail A. Filatov ◽  
Safakath Karuthedath ◽  
Pavel M. Polestshuk ◽  
Susan Callaghan ◽  
Keith J. Flanagan ◽  
...  
Keyword(s):  
Excited State ◽  
Triplet State ◽  
State Formation ◽  
Heavy Atom ◽  
Molecular Rotation ◽  
Structural Factors ◽  
Triplet Excited State ◽  
State Generation

Heavy atom-free BODIPY–anthracene dyads show triplet excited state formation via PeT, controlled by molecular rotation and environmental polarity.

Synthesis, photophysicochemical studies of adjacently tetrasubstituted binaphthalo-phthalocyanines

2005 ◽  
Vol 09 (05) ◽  
pp. 316-325 ◽  
Author(s):  
Itumeleng Seotsanyana-Mokhosi ◽  
Ji-Yao Chen ◽  
Tebello Nyokong
Keyword(s):  
Excited State ◽  
Quantum Yield ◽  
Triplet State ◽  
Singlet Oxygen ◽  
Photophysical Properties ◽  
Zinc Phthalocyanine ◽  
Quantum Yields ◽  
Triplet Excited State ◽  
General Increase ◽  
Photochemical Behavior

Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.

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