Cyclic porphyrin arrays as artificial photosynthetic antenna: synthesis and excitation energy transfer

Nakamura, Yasuyuki; Aratani, Naoki; Osuka, Atsuhiro

doi:10.1039/b618854k

Cited by 397 publications

(174 citation statements)

References 58 publications

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“…Their functions include panchromatic light harvesting through most of the visible part of the solar spectrum and electron transport (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26). As another major class of multifunctional molecular materials, fullerenes (27) offer unique opportunities for stabilizing charged entities.…”

mentioning

confidence: 99%

Step-by-step self-assembled hybrids that feature control over energy and charge transfer

Grimm

Schornbaum

Jasch

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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In the current work, we have documented the use of two complementary supramolecular motifs, namely multipoint hydrogen bonding and metal complexation, as a means to control the stepby-step assembly of a panchromatically absorbing and highly versatile solar energy conversion system. On one hand, two different perylenediimides (1a/1b) have been integrated together with a metalloporphyrin (2) by means of the Hamilton receptor/cyanuric acid hydrogen bonding motif into energy transduction systems 1a•2 or 1b•2. Steady-state and time-resolved measurements corroborated that upon selective photoexcitation of the perylenediimides (1a/1b), an energy transfer evolved from the singlet excited state of the perylenediimides (1a/1b) to that of the metalloporphyrin (2). On the other hand, fullerene (3) and metalloporphyrin (2) form the electron donor-acceptor system 2•3 via axial complexation. Photophysical measurements confirm that an electron transfer prevails from the singlet excited state of 2 to the electron-accepting 3. The correspondingly formed radical ion pair state decays with a lifetime of 1.0 AE 0.1 ns. As a complement to the aforementioned, the energy transduction features of 1a•2 were combined with the electron donor-acceptor characteristics of 2•3 to afford 1a•2•3. To this end, time-resolved measurements reveal that the initially occurring energy-transfer interaction (53 AE 3 ps) between 1a/1b and 2 is followed by an electron transfer (12 AE 1 ps) from 2 to 3. From multiwavelength analyses, the lifetime of the radical ion pair state in 1a•2•3-as a product of a cascade of light-induced energy and electron transfer-was derived as 3.8 AE 0.2 ns. I n recent years, the conversion of solar energy into electrical energy has been one of the most important areas of scientific research due to the constantly growing human energy demands (1, 2). In order to design efficient, low-cost, environmentally responsible artificial photosynthetic systems, research follows the concepts of nature (3, 4). Similar to natural photosynthetic organisms (5-8), artificial systems undergo cascades of light-induced energy and electron transfer reactions. The absorbed energy is converted into chemical potential energy in the form of a radical ion pair state (9). These events take place in organized arrays of photofunctional chromophores within specifically tailored environments that allow an efficient light harvesting. As an important prerequisite, the lifetime of the excited states should be long enough to power efficient electron transfer in order to obtain radical ion pair states. Therefore, the development of panchromatically absorbing molecules with appropriate absorptive properties for light harvesting is desirable.Owing to their biological relevance and favorable properties as natural chromophores, porphyrinoids are widely used as molecular components in artificial photosynthetic systems. Their functions include panchromatic light harvesting through most of the visible part of the solar spectrum and electron transport (10-26). As another m...

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mentioning

confidence: 99%

Step-by-step self-assembled hybrids that feature control over energy and charge transfer

Grimm

Schornbaum

Jasch

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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“…Since the observed negative and positive signs of LD bands at λ max at 448 and 408 nm, respectively, originate from electronic transitions due to longer and shorter axes of the J-aggregated DP, respectively ( Figure 3c) [32], it can be expected that DP nanofibers align perpendicularly to the rotary direction. This result is also supported by the fact that the spectral pattern is the same as that of the dip-coated film sample, placed in such a way that its oriented direction is parallel to the vertical axis of the linearly polarized incident light.…”

Section: Helical Alignment Of a Supramolecular Nanofiber In A Vortex mentioning

confidence: 99%

Hydrodynamic Helical Orientations of Nanofibers in a Vortex

Tsuda

2014

Symmetry

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Abstract:In this review article, I report our recent studies on spectroscopic visualizations of macroscopic helical alignments of nanofibers in vortex flows. Our designed supramolecular nanofibers, formed through self-assemblies of dye molecules, helically align in torsional flows of a vortex generated by mechanical rotary stirring of the sample solutions. The nanofiber, formed through bundling of linear supramolecular polymers, aligns equally in right-and left-handed vortex flows. However, in contrast, a one-handedly twisted nanofiber, formed through helical bundling of the supramolecular polymers, shows unequal helical alignments in these torsional flows. When the helical handedness of the nanofiber matches that of the vortex flow, the nanofiber aligns more efficiently in the flowing fluid. Such phenomena are observed not only with the artificial helical supramolecular nanofibers but also with biological nanofibers such as double-stranded DNA.

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“…To mimic natural archetype, many chromophores were constructed into J-aggregates by self-assemble process. Among these dyes, porphyrin dyes [2] are the most popularly investigated organic dyes because of their similar molecular structure and photophysical properties with natural bacteriochlorophyll a (Bchl a) molecules [3] [4]. However, since these chromophores exhibit much less favorable optical properties, especially a rather weak photoluminescence resulting from an almost forbidden lowest-energy transition, porphyrin aggregates can compete in this regard neither with their natural chlorophyll counterparts, nor with cyanine dye-based synthetic J-aggregates.…”

Section: Introductionmentioning

confidence: 99%

Photophysical Properties of Perylenetetracarboxylic Diimide Dimers with Slipped “Face-to-Face” Stacked Structure and Different Bay Substitutions

Qingdao¹

2016

MSCE

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A series of perylenetetracarboxylic diimides (PDIs) dimers with slipped "face-to-face" stacked structure and different substituents at the bay positions have been synthesized and the molecular structures are characterized by 1 H NMR, MALDI-TOF and elemental analysis. And different substituents at the bay positions of the PDI ring bring about various steric hindrances. These different steric hindrances have caused significant differences on the absorption and emission spectra. The correlation between the photophysical properties and the molecular structure is discussed.

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Cyclic porphyrin arrays as artificial photosynthetic antenna: synthesis and excitation energy transfer

Cited by 397 publications

References 58 publications

Step-by-step self-assembled hybrids that feature control over energy and charge transfer

Step-by-step self-assembled hybrids that feature control over energy and charge transfer

Hydrodynamic Helical Orientations of Nanofibers in a Vortex

Photophysical Properties of Perylenetetracarboxylic Diimide Dimers with Slipped “Face-to-Face” Stacked Structure and Different Bay Substitutions

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