Synthesis and Study of a Sulfur Heterocycle Fused<i>p</i>-Phenylene Vinylene Conducting Polymer

Pomerantz, M. A.; Wang, Jiping; Seong, Sang Cheol; Starkey, Kyle; Nguyen, Long

doi:10.1080/10426509408034296

Cited by 3 publications

(6 citation statements)

References 12 publications

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“…This is demonstrated by the fact that no photodegradation was observed in both the transient absorption experiments and in irradiation experiments performed using low intensity laser excitation at 320 nm for up to 2 h. Hence, on the one hand, these pollutants are expected to be highly persistent in the environment under sunlight conditions. On the other hand, given the high photostability of these DBT derivatives, these compounds exhibit superior photochemical properties for their use as synthetic building blocks that can be used for applications such as OLEDs, organic field-effect transistors, and solar cells. − We hope that the experimental and computational results reported will spur the performance of advanced multiconfigurational static and dynamical simulations as well as further time-resolved and photochemical investigations of other PASH systems.…”

Section: Discussionmentioning

confidence: 99%

“…Polycyclic aromatic sulfur heterocycles (PASHs) are a known class of environmental pollutants formed from incomplete combustion processes and oil spills/sands. − Most PASHs absorb UVA and UVB solar radiation that reaches the Earth’s surface, which leads to photophysical and photochemical processes that can result in the formation of toxic and mutagenic products, hence causing concern for environmental safety. , PASHs are also commonly used as synthetic building blocks that can be tuned for applications such as organic light-emitting diodes (OLED), organic field-effect transistors, and solar cells. − However, their excited state dynamics and electronic relaxation mechanisms are not completely understood. This is an important subject of investigation, which can provide structure-photoreactivity relationships relevant to understanding the photochemical fate of PASHs in the environment as well as for tuning their photochemical properties for rational technological applications. − …”

Section: Introductionmentioning

confidence: 99%

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Excited State Dynamics of Dibenzothiophene Derivatives

Griffith,

Krul,

Hoehn

et al. 2023

J. Phys. Chem. B

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Polycyclic aromatic sulfur heterocycles are environmental pollutants formed from incomplete combustion processes and crude oil spills. Their excited state dynamics are not understood. Herein, femtosecond transient absorption is combined with steady-state spectroscopy and computational methods to elucidate the relaxation mechanisms of three dibenzothiophene derivatives. The low-energy singlet and triplet states all have ππ* character in the Franck–Condon region, and two minima were located in the S1 surface. Excitation at 320 nm populates their S1 state directly, which relaxes with lifetimes ranging from 4 to 13 ps. Most of the S1 population undergoes efficient intersystem crossing to the triplet state with lifetimes ranging from 820 ± 50 to 900 ± 30 ps. The compounds exhibit negligible nonradiative internal conversion, low fluorescence yields of 1.2 to 1.6%, and triplet yields of ca. 98%. Linear interpolation of internal coordinates reveals the chemical basis for relaxing the spin-forbidden intersystem crossing in these π-aromatic systems.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Excited State Dynamics of Dibenzothiophene Derivatives

Griffith,

Krul,

Hoehn

et al. 2023

J. Phys. Chem. B

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“…The femtosecond broadband pump-probe transient absorption used in this study is described in detail elsewhere1 [6][7][8][9][10][11][12][13][14][15][16][17][18] . Briefly, a 800 nm fundamental pulse (4.0 W, 100 fs pulse, Libra-HE from Coherent Inc.) is split into a pump and probe pulse.…”

Section: Femtosecond Broadband Transient Absorption Spectroscopymentioning

confidence: 99%

“…Most PASHs absorb UVA and UVB solar radiation that reaches the Earth's surface, which leads to photophysical and photochemical processes that can result in the formation of toxic and mutagenic products, hence, causing concern for environmental safety 4,5 . PASHs are also commonly used as synthetic building blocks that can be tuned for applications such as organic light-emitting diodes (OLED), organic field-effect transistors, and solar cells [7][8][9][10][11] . However, their excited state dynamics and electronic relaxation mechanisms are not completely understood.…”

Section: Introductionmentioning

confidence: 99%

“…However, their excited state dynamics and electronic relaxation mechanisms are not completely understood. This is an important subject of investigation, which can provide structurephotoreactivity relationships relevant to understanding the photochemical fate of PASHs in the environment, as well as, for tuning their photochemical properties for rational technological applications [7][8][9][10][11][12][13][14] .…”

Section: Introductionmentioning

confidence: 99%

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Excited State Dynamics of Dibenzothiophene Derivatives

Crespo-Hernández,

Griffith,

Krul

et al. 2023

Preprint

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Polycyclic aromatic sulfur heterocycles are environmental pollutants formed from incomplete combustion processes and crude oil spills. Their excited state dynamics are not understood. Herein, femtosecond transient absorption is combined with steady-state spectroscopy and computational methods to elucidate the relaxation mechanisms of three dibenzothiophene derivatives. The low-energy singlet and triplet states all have pipi* character in the Franck-Condon region and two minima were located in the S1 surface. Excitation at 320 nm populates their S1 state directly, which relaxes with lifetimes ranging from 4 to 13 ps. Most of the S1 population undergoes efficient intersystem crossing to the triplet state with lifetimes ranging from 820 ± 50 to 900 ± 30 ps. The compounds exhibit negligible nonradiative internal conversion, low fluorescence yields of 1.2 to 1.6%, and triplet yields of ca. 98%. Linear interpolation of internal coordinates reveals the chemical basis for relaxing the spin-forbidden intersystem crossing in these pi-aromatic systems.

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Structural and Electronic Factors Controlling the Efficiency and Rate of Intersystem Crossing to the Triplet State in Thiophene Polycyclic Derivatives

Griffrith,

Krul,

Hoehn

et al. 2024

Chemistry A European J

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Thiophene polycyclic derivatives are widely used in organic light‐emitting diodes, photovoltaics, and medicinal chemistry applications. Understanding the electronic and structural factors controlling their intersystem crossing rates is paramount for these applications to be successful. This study investigates the photophysical, electronic structure, and excited state dynamics of 1,2‐benzodiphenylene sulfide, benzo[b]naphtho[1,2‐d]thiophene, and benzo[b]naphtho[2,3‐d]thiophene in polar aprotic and non‐polar solvents. Steady‐state absorption and emission spectroscopy, femtosecond transient absorption spectroscopy, and DFT and TD‐DFT calculations are employed. Low fluorescence quantum yields of 1.2 to 2.7 % are measured in acetonitrile and cyclohexene, evidencing that the primary relaxation pathways in these thiophene derivatives are nonradiative. Linear interpolation of internal coordinates calculations predict that an S−C bond elongation reaction coordinate facilitates the efficient intersystem crossing to the T1 state. Excitation of 1,2‐benzodiphenylene sulfide and benzo[b]naphtho[1,2‐d]thiophene at 350 nm or benzo[b]naphtho[2,3‐d]thiophene at 365 nm, populates the lowest‐energy 1ππ* state, which relaxes to the 1ππ* minimum in tens of picoseconds or intersystem crosses to the triplet manifold in ca. 500 ps to 1.1 ns depending on the position at which the benzene rings are added. Excitation at 266 nm does not affect the intersystem crossing rates. Laser photodegradation experiments demonstrate that the thiophene polycyclic derivatives are highly photostable.

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Synthesis and Study of a Sulfur Heterocycle Fusedp-Phenylene Vinylene Conducting Polymer

Cited by 3 publications

References 12 publications

Excited State Dynamics of Dibenzothiophene Derivatives

Excited State Dynamics of Dibenzothiophene Derivatives

Excited State Dynamics of Dibenzothiophene Derivatives

Structural and Electronic Factors Controlling the Efficiency and Rate of Intersystem Crossing to the Triplet State in Thiophene Polycyclic Derivatives

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