Photoinduced charge separation in self-assembled cofacial pentamers of zinc-5,10,15,20-tetrakis(perylenediimide)porphyrin

Ahrens, Michael J.; Kelley, Richard F.; Dance, Zachary E. X.; Wasielewski, Michael R.

doi:10.1039/b617876f

Cited by 67 publications

(77 citation statements)

References 71 publications

(108 reference statements)

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“…Figure 20). Other ordered 2D or 3D structures containing porphyrins with J- and H- aggregates are also reported 32,108,125,260,314,328–332…”

Section: Porphyrin Nanostructures Driven By π - π Interactionsmentioning

confidence: 77%

“…Π stacking of perylene-di-carboximides on the para position of TPP drive the formation of nano-aggregates because the perylenes are coplanar with the porphyrin (Figure 19). 314 These exhibit interesting photonic properties in that the charge delocalizes in the nanoparticles. Other localized interactions such as dipolar and electrostatic interactions can be exploited to develop ordered structures on ordered surfaces.…”

Section: Porphyrin Nanostructures Driven By π - π Interactionsmentioning

confidence: 99%

“…The perylene units are electron-acceptors and promote the electronic communication between the adjacent porphyrin allowing energy or charge transfer. Self-assembly of the (ZnTPP-PDI) 4 is driven primarily by π-π interactions between the adjacent PDI and yields columnar stacks of an average of five cofacial molecules314…”

Section: Figures and Tablementioning

confidence: 99%

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Self-Organized Porphyrinic Materials

2009

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The self-assembly and self-organization of porphyrins and related macrocycles enables the bottomup fabrication of photonic materials for fundamental studies of the photophysics of these materials and for diverse applications. This rapidly developing field encompasses a broad range of disciplines including molecular design and synthesis, materials formation and characterization, and the design and evaluation of devices. Since the self-assembly of porphyrins by electrostatic interactions in the late 1980s to the present, there has been an ever increasing degree of sophistication in the design of porphyrins that self-assemble into discrete arrays or self-organize into polymeric systems. These strategies exploit ionic interactions, hydrogen bonding, coordination chemistry, and dispersion forces to form supramolecular systems with varying degrees of hierarchical order. This review concentrates on the methods to form supramolecular porphyrinic systems by intermolecular interactions other than coordination chemistry, the characterization and properties of these photonic materials, and the prospects for using these in devices. The review is heuristically organized by the predominant intermolecular interactions used and emphasizes how the organization affects properties and potential performance in devices.

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“…Figure 20). Other ordered 2D or 3D structures containing porphyrins with J- and H- aggregates are also reported 32,108,125,260,314,328–332…”

Section: Porphyrin Nanostructures Driven By π - π Interactionsmentioning

confidence: 77%

Section: Porphyrin Nanostructures Driven By π - π Interactionsmentioning

confidence: 99%

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Self-Organized Porphyrinic Materials

2009

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“…In this figure, we show that the observed rate constant for ultrafast exciton decay (1/τ 1 ) is approximately a linear function of the number of bound TCNQ x-per QD, a dependence characteristic of charge transfer in single donor-multi-acceptor systems composed of nanoparticles, [22,23] and molecular redox centers. [24] In order to support the concerted charge transfer mechanism for PL quenching, and to clarify the roles of both TCNQ x-and the surface hole formed upon the spontaneous reduction of TCNQ in this mechanism, we added pre-electrolyzed TCNQ 1-(with tetrabutylammonium, TBA + , counterion) to the QDs rather than allowing the TCNQ to be reduced in situ. When we add 2.5 equivalents of TBA + /TCNQ 1-to 1.7 µM PbS QDs in CHCl 3 , we observe that 3.4% of the sample's PL is quenched, whereas 40% of the sample's PL is quenched when we add this same number of equivalents of TCNQ to the QDs in solution, (see the Supporting Information, Figure S14).…”

Section: Figure 1 A)mentioning

confidence: 99%

Ultrafast exciton decay in PbS quantum dots through simultaneous electron and hole recombination with a surface-localized ion pair

et al. 2016

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This paper describes the ultrafast decay of the band-edge exciton in PbS quantum dots (QDs) through simultaneous recombination of the excitonic hole and electron with the surface localized ion pair formed upon adsorption of tetracyanoquinodimethane (TCNQ). Each PbS QD (R= 1.8 nm) spontaneously reduces up to 17 TCNQ molecules upon adsorption of the TCNQ molecule to a sulfur on the QD surface. The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast (≤15 ps) non-radiative decay of the exciton; the rate constant for the decay process increases approximately linearly with the number of adsorbed, reduced TCNQ molecules. Near-infrared and mid-infrared transient absorption show that this decay occurs through simultaneous transfer of the excitonic electron and hole, and is assigned to a four-carrier, concerted charge recombination mechanism based on the observations that (i) the PL of the QDs recovers when spontaneously reduced TCNQ 1-desorbs from the QD surface upon addition of salt, and (ii) the PL of the QDs is preserved when another spontaneous oxidant, ferrocinium, which cannot participate in charge transfer in its reduced state, is substituted for TCNQ.2

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“…In supramolecular chemistry the formation of non‐discrete porphyrin aggregates has been studied in great detail, taking advantage of π‐stacking, hydrogen bonding, metal–ligand and hydrophobic interactions to create functional multi‐chromophoric aggregates. For example, the group of Wasielewski reported on the self‐assembly of Zn‐porphyrins appended with four perylene bisimides into either one‐ or two‐dimensional aggregates depending on the perylene bay substituents . Nolte and co‐workers investigated the self‐assembly of porphyrin‐functionalized benzene‐1,3,5‐tricarboxamides, in which three non‐symmetrical porphyrins were connected by amide linkages to a benzene core .…”

Section: Introductionmentioning

confidence: 99%

Directing the Self‐Assembly Behaviour of Porphyrin‐Based Supramolecular Systems

Weegen

Teunissen

Meijer

2017

Chemistry A European J

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The self-assembly behaviour of a library of tetra-amidated porphyrin molecules decorated with a variety of solubilizing wedges is investigated as dilute solutions in methylcyclohexane. Small changes in the solubilising wedge of the porphyrins resulted in different aggregated states, as evidenced by CD and UV/Vis absorption spectroscopy. The porphyrins form co-facially stacked H-aggregates, slip-stacked J-aggregates or a mixture of both. Detailed thermodynamic and kinetic analysis showed that in all cases the formation of J-aggregates proceeds via an isodesmic mechanism whereas H-aggregates are formed via a cooperative mechanism. It is shown that these aggregates assemble in a parallel pathway, in which both compete for the monomer, compared to a sequential pathway, in which one of the aggregates interconverts into the other. Interestingly, kinetic analysis of porphyrins that only form H-aggregates in thermodynamic equilibrium revealed that the competing pathway towards J-aggregates is operational in these systems as well. Our findings show that the balance between H- and J-aggregates depends on remarkably small changes in the architecture of the solubilising wedges.

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Photoinduced charge separation in self-assembled cofacial pentamers of zinc-5,10,15,20-tetrakis(perylenediimide)porphyrin

Cited by 67 publications

References 71 publications

Self-Organized Porphyrinic Materials

Self-Organized Porphyrinic Materials

Ultrafast exciton decay in PbS quantum dots through simultaneous electron and hole recombination with a surface-localized ion pair

Directing the Self‐Assembly Behaviour of Porphyrin‐Based Supramolecular Systems

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