Quenching of the triplet state of tetrapyrrole molecules by Ni-, Ag-, and Fe-porphyrins and formation of excited complexes and photoproducts

2000 ◽  
Vol 67 (3) ◽  
pp. 405-411
Author(s):  
V. V. Sapunov
Author(s):  
Dmitriy N. Gurulev ◽  
Lyubov V. Palatkina ◽  
Anna S. Yudina ◽  
Vladimir I. Porkhun

To date, it is considered established that quinones with lower energy state, under the action of light tear away a hydrogen atom from a hydrocarbon or an electron donor from inorganic anion-radicals, which have a high reduction potential. However, even for the simplest quinones (1,4-benzoquinone, 1,4-naphthoquinones, 9,10-anthraquinone and their derivatives) there is no consensus in the science literature about the nature of the initial event in photoreaction with compounds which are potential donors of hydrogen atom and electron. The first step in many photochemical reactions is the formation of complexes between donors and acceptors of electrons in the excited state (exiplexes). Photoreactive quinones as elementary acts include the transfer of electron (or) hydrogen atom. The mechanism depends on the presence and strength of donor-acceptor complexes (DAC) of the quinones with the reagents. Studies of triplet exiplexes allow you to set the details of the elementary reaction acts. Only short-lived intermediate product was registered upon photoexcitation of the studied quinone Q in low-polarity solvents. The kinetic of decay of the first order with rate constant of about 2∙106 s-1 in toluene and dibutylphthalate and the introduction of oxygen leads to a decrease in the lifetime of the product in the triplet state. With the introduction of solutions of amines quenching of triplet state (QT) with rate constant close to diffusion was observed. Rate constants of quenching by dissolving in benzene and by dissolving in dibutyl phthalate were determined. It is established that formation of intermediate products is carried out from triplet state (QT). Excited complexes with charge transfer in acetonitrile were not observed. It is concluded that with decrease in electron affinity of the acceptors, when the connection of the molecules in the complex becomes weaker, the lifetime of TE increases significantly.


2020 ◽  
Vol 56 (43) ◽  
pp. 5819-5822
Author(s):  
Jing Zheng ◽  
Yongzhuo Liu ◽  
Fengling Song ◽  
Long Jiao ◽  
Yingnan Wu ◽  
...  

In this study, a near-infrared (NIR) theranostic photosensitizer was developed based on a heptamethine aminocyanine dye with a long-lived triplet state.


2002 ◽  
Vol 76 (5) ◽  
pp. 480 ◽  
Author(s):  
Xavier Damoiseau ◽  
Francis Tfibel ◽  
Maryse Hoebeke ◽  
Marie-Pierre Fontaine-Aupart

2019 ◽  
Author(s):  
Madhumita Rano ◽  
Sumanta K Ghosh ◽  
Debashree Ghosh

<div>Combining the roles of spin frustration and geometry of odd and even numbered rings in polyaromatic hydrocarbons (PAHs), we design small molecules that show exceedingly small singlet-triplet gaps and stable triplet ground states. Furthermore, a computationally efficient protocol with a model spin Hamiltonian is shown to be capable of qualitative agreement with respect to high level multireference calculations and therefore, can be used for fast molecular discovery and screening.</div>


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