Synthesis and Optical Properties of Bacteriochlorophyll-<i>a</i> Derivatives Having Various C3 Substituents on the Bacteriochlorin π-System

Sasaki, Shin‐ichi; Tamiaki, Hitoshi

doi:10.1021/jo0523969

Cited by 68 publications

(52 citation statements)

References 30 publications

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“…The way in which bacteriochlorophyll (BChl) molecules self-assemble to form the light-harvesting complexes found in the chlorosomes of green sulfur bacteria, however, remains a subject of debate in the absence of Xray crystallographic evidence. In particular, Tamiaki and coworkers [8,[84][85][86][87] and Balaban et al [7,[88][89][90] have put much effort in devising (semi-)synthetic mimics of self-assembling BChl units to investigate the self-assembling structures. Balaban recently made a very convincing case for a model, in which BChl monomers are assumed to selfassemble through intermolecular interactions between the central magnesium atom of one BChl molecule, the ketone oxygen atom of one of its BChl neighbors, and the hydroxy oxygen atom of the other neighbor (Figure 14, right).…”

Section: Relevance To Biological Systemsmentioning

confidence: 99%

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

Suijkerbuijk

Tooke

Spek

et al. 2007

Chemistry An Asian Journal

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A series of meso-tetrakis-(ERE donor) zinc(II) porphyrins nZn (ERE donor = 4-R-3,5-bis[(E)-methyl]phenyl; 1Zn: E = NMe2, R = Br; 2Zn: E = NMe2, R = H; 3Zn: E = OMe, R = Br; 4Zn: E = OMe, R = H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of nZn self-assemble to form one-dimensional porphyrin polymers [nZn](infinity) in the solid state, as confirmed for 1Zn and 3Zn by X-ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E = N, O) provided by the EBrE donor groups of adjacent nZn molecules. Complexes 2Zn and 4Zn did not form single crystals, but solid-state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and 1H NMR spectroscopy indicated that interactions between 1Zn and 2Zn monomers in the polymers are stronger than between 3Zn and 4Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the nZn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc-zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies.

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Section: Relevance To Biological Systemsmentioning

confidence: 99%

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

Suijkerbuijk

Tooke

Spek

et al. 2007

Chemistry An Asian Journal

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“…Although inherently limited by the presence of nearly a full complement of substituents arrayed about the perimeter of the macrocycle, numerous studies have exploited this approach to probe the role of diverse substituents about the chlorin macrocycle (6)(7)(8)(9)(10)(11)(12)(13)(14)(15). A major challenge toward semisynthesis of bacteriochlorophylls resides in the intrinsic lability of the molecules (16)(17)(18)(19)(20)(21)(22). (iii) De novo synthesis: This approach, which we have pursued, entails the total synthesis of chlorins and bacteriochlorins from simple, commercially available precursors.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photophysical Characterization of Porphyrin, Chlorin and Bacteriochlorin Molecules Bearing Tethers for Surface Attachment

Muthiah

Taniguchi

Kim

et al. 2007

Photochem & Photobiology

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The ability to tailor synthetic porphyrin, chlorin and bacteriochlorin molecules holds promise for diverse studies in artificial photosynthesis. Toward this goal, the synthesis and photophysical characterization of five tetrapyrrole compounds is described. Each compound bears a surface attachment group. One set contains three meso-substituted porphyrins that differ only in the nature of a surface-binding tether-isophthalic acid, ethynylisophthalic acid or cyanoacrylic acid. The other set includes a porphyrin, chlorin and bacteriochlorin each of which bears an ethynylisophthalic acid tether. The ester derivative of each compound was prepared for solution photophysical characterization studies. The photophysical studies include determination (in toluene or acetonitrile) of the electronic absorption and fluorescence spectra, fluorescence yield and lifetime of the lowest excited singlet state. The excited-state lifetimes range from 1 to 5.6 ns for the five compounds. The radiative rate constant for the excited-state decay was estimated from the photophysical data (fluorescence yield and excited-state lifetime) and from Strickler-Berg analysis of the absorption and fluorescence spectra. The synthesis and characterization of the tetrapyrrole compounds underpin their use as sensitizers in molecular-based solar cells.

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“…[12] Unlike chlorophylls found in plants,b acteriochlorophylls have absorption spectra that are principally centered in the nearinfrared region of the light spectrum. [12] Unlike chlorophylls found in plants,b acteriochlorophylls have absorption spectra that are principally centered in the nearinfrared region of the light spectrum.…”

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confidence: 99%

Light‐Regulated Polymerization under Near‐Infrared/Far‐Red Irradiation Catalyzed by Bacteriochlorophyll a

2015

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Photoregulated polymerizations are typically conducted using high-energy (UV and blue) light, which may lead to undesired side reactions. Furthermore, as the penetration of visible light is rather limited, the range of applications with such wavelengths is likewise limited. We herein report the first living radical polymerization that can be activated and deactivated by irradiation with near-infrared (NIR) and far-red light. Bacteriochlorophyll a (Bachl a) was employed as a photoredox catalyst for photoinduced electron transfer/reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Well-defined polymers were thus synthesized within a few hours under NIR (λ=850 nm) and far-red (λ=780 nm) irradiation with excellent control over the molecular weight (M(n)/M(w)<1.25). Taking advantage of the good penetration of NIR light, we showed that the polymerization also proceeded smoothly when a translucent barrier was placed between light source and reaction vessel.

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Synthesis and Optical Properties of Bacteriochlorophyll-a Derivatives Having Various C3 Substituents on the Bacteriochlorin π-System

Cited by 68 publications

References 30 publications

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

Synthesis and Photophysical Characterization of Porphyrin, Chlorin and Bacteriochlorin Molecules Bearing Tethers for Surface Attachment

Light‐Regulated Polymerization under Near‐Infrared/Far‐Red Irradiation Catalyzed by Bacteriochlorophyll a

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