Directly Linked Porphyrin Arrays with Tunable Excitonic Interactions.

Kim, Dongho; Osuka, Atsuhiro

doi:10.1002/chin.200502248

Cited by 18 publications

(25 citation statements)

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“…Many of these designs incorporate porphyrin-based molecules (17)(18)(19)(20)(21)(22), a pigment that is related to the ubiquitous chlorophyll found in natural light-harvesting systems (23). Porphyrins possess characteristic structural and photophysical properties that make them well suited for adaptation into artificial designs, not only for solar energy conversion but also for applications in photodynamic therapy (24)(25)(26)(27)(28)(29), enzyme mimics (30)(31)(32), catalysis (33)(34)(35)(36)(37), and molecular electronic devices (38,39).…”

mentioning

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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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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“…Various types of covalently linked arrays of metallo porphyrins have been designed and synthesized with the goal of applying these molecular oligomers to molecular photonic devices [26,52,[59][60][61][62] as artificial light-harvesting systems [34,[62][63][64][65]. Among them, meso-meso linked porphyrinic arrays have been emerged as an interesting candidate for exploring the artificial photosynthetic reaction centers and light harvesting antenna complexes (Figure 1).…”

Section: Meso-meso Linked Porphyrin Arraysmentioning

confidence: 99%

“…These approaches include covalent synthesis [26,27], and self-assembly by metal coordination [28][29][30] or hydrogen bonding [31][32][33]. Covalent linking is the most classical and productive method for the synthesis of such chemical models [34,35].…”

Section: Multiporphyrins As Chemical Models For Photosynthesismentioning

confidence: 99%

Meso-Linked Multiporphyrins as Model for Light Harvesting Systems: Review

Singhal¹

2017

Nat Prod Chem Res

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Nature has always been the fundamental source of inspiration for researchers to understand the complex biological functions. Photosynthesis is among the important natural phenomena and hence, gained interest towards developing the artificial photosynthetic reaction centers. Electron and energy transfer process between various porphyrin units within the multiporphyrin arrays is the important key in developing such systems. Long duration of charge separated state and spectral coverage scope of the accepting porphyrin units are another important factor that contribute to an efficient mimic of the photosynthetic reaction center. Meso-linked porphyrin architectures provide a great aspect in this regard because of short inter-porphyrinic distance with optimal dihedral angle. The present review highlights the design of various kinds of meso-linked multiporphyrins and study of electron and energy transfer processes between them that serve as an efficient model for light harvesting systems.

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“…With the discovery of intricate structures of photosynthetic light harvesting complexes10,32 and the progress in the capability to synthesize new macromolecules or nanometer‐scale assemblies, it has become an important issue to understand the dynamics of excitons among tens or hundreds of chromophores arranged in a nontrivial manner 13,33–39. If the couplings between chromophores are weak, the dynamics of exciton can be described by rate processes as in the case of porphyrin arrays 40. However, in general, excitons are delocalized and their behavior depends sensitively on electronic couplings, electron–phonon interactions, and the disorder.…”

Section: Introductionmentioning

confidence: 99%

Resonance energy flow dynamics of coherently delocalized excitons in biological and macromolecular systems: Recent theoretical advances and open issues

Jang

Cheng

2012

WIREs Comput Mol Sci

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Recent experimental and theoretical studies suggest that biological photosynthetic complexes utilize the quantum coherence in a positive manner for efficient and robust flow of electronic excitation energy. Clear and quantitative understanding of such suggestion is important for identifying the design principles behind efficient flow of excitons coherently delocalized over multiple chromophores in condensed environments. Adaptation of such principles for synthetic macromolecular systems has also significant implication for the development of novel photovoltaic systems. Advanced theories of resonance energy transfer are presented, which can address these issues. Applications to photosynthetic light harvesting complex systems and organic materials demonstrate the capabilities of new theoretical approaches and future challenges. C 2012 John Wiley & Sons, Ltd.

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Directly Linked Porphyrin Arrays with Tunable Excitonic Interactions.

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 18 publications

References 1 publication

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

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

Meso-Linked Multiporphyrins as Model for Light Harvesting Systems: Review

Resonance energy flow dynamics of coherently delocalized excitons in biological and macromolecular systems: Recent theoretical advances and open issues

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