Hard–Soft Acid–Base Theory Explains Photoexcited Carrier Dynamics in Porphyrin/CNT Nanohybrids: Time-Domain Atomistic Analysis DOI Creative Commons

Uttam Kumar Chowdhury,

Shrabanti Mondal, Subhajit Dey

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

We employ the fundamental chemical concepts of hard-soft acid-base to formulate general principles governing excited-state dynamics in zinc porphyrin (ZnP)/carbon nanotube (CNT) hybrids for energy photoconversion. Atomistic quantum simulations demonstrate that electron-withdrawing and donating substituents at ZnP β-pyrrolic position strongly influence dynamics. photoexcitation produces subpicosecond electron transfer (ET) from CNT, agreement with experiment. Substitutions CN by H tBu accelerate ET. The trend is directly related concept because soft-soft interaction between tBu-ZnP acid mild CNT base enhances donor-acceptor coupling. Longer coherence more active vibrational modes facilitate ET tBu-ZnP/CNT. Electron-hole recombination CN-ZnP/CNT occurs on a hundred picosecond time scale, nicely corroborated exciton lifetime extended beyond nanosecond substitutions. tBu-ZnP/CNT increases splitting highest occupied orbitals two subsystems, reduces their mixing, decreases nonadiabatic coupling ground excited states. Rapid decoherence involvement low-frequency vibrations favor longer lifetimes. Our investigation reveals larger pKa gives rapid slow provides detailed mechanistic information, essential future optoelectronic applications.

Язык: Английский

Self-assembly behaviour of heterocyclic polymers induced by multiple carbon cone molecules DOI

X.P. Zhang,

Danhui Zhang, Wenqiang Hu

и другие.

Journal of Solid State Chemistry, Год журнала: 2025, Номер 350, С. 125458 - 125458

Опубликована: Июнь 4, 2025

Язык: Английский

Процитировано

0
Hard–Soft Acid–Base Theory Explains Photoexcited Carrier Dynamics in Porphyrin/CNT Nanohybrids: Time-Domain Atomistic Analysis DOI Creative Commons

Uttam Kumar Chowdhury,

Shrabanti Mondal, Subhajit Dey

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

We employ the fundamental chemical concepts of hard-soft acid-base to formulate general principles governing excited-state dynamics in zinc porphyrin (ZnP)/carbon nanotube (CNT) hybrids for energy photoconversion. Atomistic quantum simulations demonstrate that electron-withdrawing and donating substituents at ZnP β-pyrrolic position strongly influence dynamics. photoexcitation produces subpicosecond electron transfer (ET) from CNT, agreement with experiment. Substitutions CN by H tBu accelerate ET. The trend is directly related concept because soft-soft interaction between tBu-ZnP acid mild CNT base enhances donor-acceptor coupling. Longer coherence more active vibrational modes facilitate ET tBu-ZnP/CNT. Electron-hole recombination CN-ZnP/CNT occurs on a hundred picosecond time scale, nicely corroborated exciton lifetime extended beyond nanosecond substitutions. tBu-ZnP/CNT increases splitting highest occupied orbitals two subsystems, reduces their mixing, decreases nonadiabatic coupling ground excited states. Rapid decoherence involvement low-frequency vibrations favor longer lifetimes. Our investigation reveals larger pKa gives rapid slow provides detailed mechanistic information, essential future optoelectronic applications.

Язык: Английский

Процитировано

0