Energy and electron transfer properties of methyl pheophorbide-a in zinc porphyrin-pheophorbide dyads

doi:10.1016/S0040-4020(97)00902-2

Tetrahedron

Volume 53, Issue 40, 6 October 1997, Pages 13657-13666

https://doi.org/10.1016/S0040-4020(97)00902-2 Get rights and content

Abstract

A series of ortho-, meta- and para-substituted zinc porphyrin-pheophorbide dyads were synthesized directly from methyl pheophorbide-a by trans-esterification of β-keto methyl ester with hydroxymethyl substituted porphyrins. Quantitative energy transfer occurred from the excited zinc porphyrin to the pheophorbide. The excited state of the pheophorbide was quenched by an electron transfer reaction from the zinc porphyrin that was found to depend both on the distance between chromophores and the polarity of solvent.

Zinc porphyrin-pheophorbide hybrid dyads were directly synthesized from methyl pheophorbide-a and their photochemical properties were investigated.

References (16)

R. Van Grondelle et al.
Biochim. Biophys. Acta
(1994)
M. Raghavan et al.
Chem. Phys. Lett.
(1993)
S. Shinoda et al.
Tetrahedron Lett.
(1996)
T. Asahi et al.
J. Am. Chem. Soc.
(1993)
K. Maruyama et al.
Pure Appl. Chem.
(1990)
A. Osuka et al.
J. Am. Chem. Soc.
(1993)
M.R. Wasielewski
Chem. Rev.
(1992)

There are more references available in the full text version of this article.

Cited by (24)

Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor<inf>1</inf>-acceptor<inf>2</inf> systems for artificial photosynthesis
2017, Tetrahedron
Citation Excerpt :
Characterization studies were performed at the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University. 4,4,5,5-tetramethyl-2-(perylen-3-yl)-1,3,2-dioxaborolane (1.23 g, 3.25 mmol),23 4-bromo-2,5-dimethylbenzenamine (0.78 g, 3.9 mmol), and sodium carbonate (1.38 g, 13 mmol) were place in round bottom 2-neck 250 mL flask in mixed solvent (toluene/water = 20 mL/6 mL) equipped with reflux condenser. Pd(PPh3)4 was added to the reaction mixture and heated to reflux for 20 h under N2 atmosphere.
We report the synthesis and photophysical characterization of isomeric donor-acceptor₁-acceptor₂ (D-A₁-A₂) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A₁) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A₂) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per^+• and NDI^‒• simultaneously with time constants of ∼50 ps in benzonitrile and ∼80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from ^1*Per to NDI and is consistent with a two-step mechanism, ^1*Per-Xy-NMI-x-NDI → Per^+•-Xy-NMI^‒•-x-NDI → Per^+•-Xy-NMI-x-NDI^‒•, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.
Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads
2016, Journal of Luminescence
Citation Excerpt :
Photosynthetic organisms use a special multi-chromophoric assembly to capture sunlight, as shown in light-harvesting complex LH2 [1]. Although various energy transfer systems containing porphyrins have been synthesized and investigated so far, many porphyrin systems had donor and/or an acceptor of excitation energy on their inter-planer positions [2–13]. Since antenna chlorophyll dimers in the LH2 were stacked from axial direction [1], an energy transfer (ENT) system with π-π interaction should be investigated to understand the efficient ENT.
Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process.
β-Keto ester aminolysis of pheophorbide a methyl ester: a facile route for asymmetric chlorin ring substitution
2010, Tetrahedron Letters
Synthesis of stereospecifically face-protected chlorophyll derivatives
2005, Tetrahedron Letters
Sugar building-block as a fine-tunable link for electron-donor- electron-acceptor couples
1999, Tetrahedron Letters
Self-organization principles in the formation of multiporphyrin complexes and semiconductor quantum dot-porphyrin nanoassemblies
2014, Journal of Porphyrins and Phthalocyanines

View all citing articles on Scopus

View full text

Energy and electron transfer properties of methyl pheophorbide-a in zinc porphyrin-pheophorbide dyads

Abstract

Biochim. Biophys. Acta

Chem. Phys. Lett.

Tetrahedron Lett.

J. Am. Chem. Soc.

Pure Appl. Chem.

J. Am. Chem. Soc.

Chem. Rev.