Intramolecular Energy Transfer within Butadiyne-Linked Chlorophyll and Porphyrin Dimer-Faced, Self-Assembled Prisms

Kelley, Richard F.; Lee, Suk Joong; Wilson, Thea M.; Nakamura, Yasuyuki; Tiede, David M.; Osuka, Atsuhiro; Hupp, Joseph T.; Wasielewski, Michael R.

doi:10.1021/ja075494f

Cited by 117 publications

(66 citation statements)

References 66 publications

(128 reference statements)

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“…720 The butadiyne-linked dimers, upon treatment with three-fold symmetric ligands such as triethynylpyridine, assembled into prismatic structures in which the dimers comprised the faces of the prism. The incorporation of butadiyne linkages increased the ability of these dimers to absorb the solar spectrum over a broad range of wavelengths.…”

Section: Miscelleneousmentioning

confidence: 99%

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

2011

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Section: Miscelleneousmentioning

confidence: 99%

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

2011

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“…1073/pnas.1408905111/-/DCSupplemental. supramolecular coordination complexes in traditional one-or two-component schemes (50)(51)(52)(53).…”

Section: Significancementioning

confidence: 99%

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

Shi

Sánchez‐Molina

Cao

et al. 2014

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

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Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90°Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by 31 P and 1 H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP. supramolecular chemistry | metallacages T he use of sunlight is ubiquitous as the input for carbonneutral, renewable energy schemes (1). Every strategy that relies on solar energy conversion, ranging from direct conversion to electricity in photovoltaics (2) to the generation of fuels via electrocatalysis (3), photoanode (4, 5), or photocathode devices (6), or photocatalysis (7) requires that photons be absorbed by a molecule or material as the first step in providing the driving force for subsequent transformation. Natural systems have evolved light-harvesting complexes, comprising multiprotein ensembles embedded with pigment molecules to enhance photon absorption for photosynthesis (8). These pigment-rich sites are arranged such that excitation of a distal chromophore will ultimately result in energy transfer to a reaction center via a series of migration and transfer processes (9). Strategies to replicate natural light-harvesting complexes necessarily demand the organization of multiple chromophores (10), a requirement that makes self-assembly and supramolecular chemistry particularly well suited for such efforts (11-13). As such, a variety of approaches have been applied toward the development of new materials that exhibit broadband absorption and efficient energy transfer (14-16). The subsequent studies of such materials span investigations of the fundamental science behind energy migration and transfer, t...

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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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Intramolecular Energy Transfer within Butadiyne-Linked Chlorophyll and Porphyrin Dimer-Faced, Self-Assembled Prisms

Cited by 117 publications

References 66 publications

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

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

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