Energy-transfer studies on phthalocyanine–BODIPY light harvesting pentad by laser flash photolysis

2015 ◽  
Vol 19 (01-03) ◽  
pp. 261-269 ◽  
Author(s):  
Mohamed E. El-Khouly ◽  
Cem Göl ◽  
Morad M. El-Hendawy ◽  
Serkan Yeşilot ◽  
Mahmut Durmuş

A molecular pentad, comprised of zinc phthalocyanine ( ZnPc ) with four boron dipyrromethene units (BODIPY) have been examined by femtosecond and nanosecond laser flash photolysis to explore its photoinduced intramolecular events from the excited BODIPY. The geometry optimization showed that the phthalocyanine moiety is completely symmetric and form perfect square planar complex with zinc. The absorption spectrum of ZnPc -BODIPY pentad covers most of the visible region (ca. 300–750 nm), which clearly is an advantage for capturing solar energy. The excitation transfer from the singlet BODIPY to ZnPc is envisioned due to good spectral overlap of the BODIPY emission and ZnPc absorption spectra. Femtosecond laser flash photolysis studies provided concrete evidence for the occurrence of energy transfer from the singlet excited BODIPY to ZnPc in tetrahydrofuran. The kinetic study of energy transfer measured by monitoring the decay of the BODIPY emission revealed fast energy transfer (5.90 × 1010 s-1) in the molecular pentad. Since the electron transfer from the singlet ZnPc to BODIPY is thermodynamically not feasible, the singlet ZnPc decayed to populates the triplet ZnPc , in addition to the grounds state. These findings suggest the potential of the examined ZnPc -BODIPY pentad to be efficient photosynthetic antenna in the artificial photosynthetic systems.

RSC Advances ◽  
2020 ◽  
Vol 10 (42) ◽  
pp. 24817-24829 ◽  
Author(s):  
Janina Kabatc ◽  
Katarzyna Iwińska ◽  
Alicja Balcerak ◽  
Dominika Kwiatkowska ◽  
Agnieszka Skotnicka ◽  
...  

The chemical mechanisms were investigated by steady state photolysis and nanosecond laser flash photolysis experiments. A mechanism for initiating polymerization using both onium salts is proposed here.


2005 ◽  
Vol 34 (11) ◽  
pp. 1522-1523 ◽  
Author(s):  
Takashi Tachikawa ◽  
Tatsuto Yui ◽  
Mamoru Fujitsuka ◽  
Katsuhiko Takagi ◽  
Tetsuro Majima

1989 ◽  
Vol 67 (6) ◽  
pp. 967-972 ◽  
Author(s):  
R. Minto ◽  
A. Samanta ◽  
P.K. Das

1-Thiobenzoylnaphthalene (TBN), known for its pericyclization reaction from the lowest excited singlet state (S1), has been subjected to nanosecond and picosecond laser flash photolysis studies. The two major transients observed in the course of nanosecond laser pulse excitation are (i) the short-lived triplet characterized by two absorption maxima (400–410 and 740–750 nm) and submicrosecond intrinsic lifetimes (80–130 ns) and (ii) a relatively long-lived species (λmax = 520 nm and τ = 220–240 ns). Various triplet-related photophysical data of TBN, including self-quenching and bimolecular quenching rate constants, have been determined. The existence of a photochemical path from S1 manifests itself in low intersystem crossing quantum yields, particularly in the polar/hydrogen-bonding solvent, methanol. From the build-up of the triplet under picosecond excitation into S1 the lifetime of the latter is estimated to be ≤ 50 ps (in benzene). The fast intrinsic decay of TBN triplet is attributable to facile intra- and intermolecular photochemistry. The 520 nm transient species could not be definitively assigned, except that it is neither a triplet nor a triplet-derived product and that it arises via photochemistry from S1. Keywords: laser flash photolysis, triplet, transients, absorption maxima, lifetimes, quenching rate constants, photochemistry, 1-thiobenzoylnaphthalenes.


2003 ◽  
Vol 81 (6) ◽  
pp. 799-806 ◽  
Author(s):  
N P Schepp ◽  
Y Rodríguez-Evora

Nanosecond laser flash photolysis of coniferyl alcohol and isoeugenol in acetonitrile leads to the formation of transient species that are identified as the corresponding radical cations. These radical cations decay with rate constants of ca. 1 × 106 s–1 in dry acetonitrile. Both radical cations react rapidly with hydroxylic solvents like water and alcohols to give 4-vinylphenoxyl radicals, indicating that these reagents behave as bases rather than nucleophiles. In addition, anionic reagents (acetate, cyanide, and chloride) react rapidly with the radical cations with second-order rate constants that are close to diffusion controlled. The main products generated in the presence of the anionic reagents are again the 4-vinylphenoxyl radicals, suggesting that these reagents also behave as bases. The lifetime of the radical cations in acidic acetonitrile was found to increase dramatically due to a shift in the radical cation – vinyl phenoxyl radical acid–base equilibrium to the side of the radical cation. An estimate of the pKa of the radical cation in acetonitrile of 4.0 was obtained from the data.Key words: radical cations, laser flash photolysis, lignan, vinylphenols.


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