Perylene Acceptor Research Articles

Tuning the triplet population of arylselanyl-BODIPY photosensitizers through substituents engineering for triplet-triplet annihilation photon upconversion with perylene

Organic triplet-triplet annihilation photon upconversion (TTA-UC) systems have attracted considerable attention owing to their promising applicability in solar energy harvesting, optoelectronic devices, photocatalysts, and bio-imaging. In this study, a series of BODIPYs prepared by incorporating substituted/ unsubstituted arylselenium groups, 1 (R = H), 2 (R = OMe), and 3 (R = F), were evaluated as triplet photosensitizers for TTA-UC. Direct Se-C bond formation on the BODIPY core provided a facile intersystem crossing (ISC) channel from the excited singlet state to the metastable triplet state, being the most effective in 2, as inferred from the singlet oxygen generation experiments, possibly because of the n-electron arising from the OMe group. The UC behavior of systems comprising the sensitizers and perylene as the acceptor in deaerated toluene was investigated using a 524 nm-wavelength laser to detect upconverted emission at 449 nm; thus, the UC yield decreased in the order of 21% for 3 > 16% for 2 > 12% for 1. This trend is consistent with the Stern-Volmer constants calculated from the quenched triplet state lifetimes of the sensitizers as a function of the concentration of the perylene quencher. This suggests that the UC efficiency was mainly governed by the intermolecular triplet-triplet energy transfer (TTET) process between arylselanyl-BODIPY photosensitizers and the perylene acceptor. This result was rationalized by the efficient population of the long-lived triplet excited state of the sensitizer, which is advantageous for diffusion-controlled TTA-UC behavior.

Layered silicate edge-linked perylene diimides: Synthesis, self-assembly and energy transfer

The control over intermolecular interactions between chromophores at nanomaterial interfaces is important for sensing and light-harvesting applications. To that aim, inorganic nanoparticles with anisotropic shape and surface chemistry can serve as useful supports for organic modification. Herein, novel asymmetric perylene diimides with aspartic acid and oleyl terminal groups were grafted to the edges of the layered silicate clay Laponite, a water-dispersible discoidal nanoparticle. The photophysical properties and solvent-dependent self-assembly of the nanoclay-grafted perylenes were investigated, revealing that the polarity of the terminating ligand dictates the aggregation behavior in aqueous solution, where increased water content generally led to the formation of perylene H-aggregates. The anionic basal surface of the nanoclay provided a binding site for a cationic fluorophore, leading to energy transfer from the face-bound donor to the edge-bound perylene acceptor. This study encourages further research on the use of functional ligands for the formation of organic–inorganic hybrids, particularly where inorganic template particles with specific surface chemistry can be exploited to study intermolecular interactions. Overall, these findings should advance further design and implementation of novel semiconducting ligands towards inorganic–organic hybrids, with potential applications in sensing and energy harvesting.

Photoinduced Energy Transfer in Linear Guest-Host Chromophores: A Computational Study.

Polymer-based guest-host systems represent a promising class of materials for efficient light-emitting diodes. The energy transfer from the polymer host to the guest is the key process in light generation. Therefore, microscopic descriptions of the different mechanisms involved in the energy transfer can contribute to enlighten the basis of the highly efficient light harvesting observed in this kind of materials. Herein, the nature of intramolecular energy transfer in a dye-end-capped conjugated polymer is explored by using atomistic nonadiabatic excited-state molecular dynamics. Linear perylene end-capped (PEC) polyindenofluorenes (PIF), consisting of n (n = 2, 4, and 6) repeat units, i.e., PEC-PIFn oligomers, are considered as model systems. After photoexcitation at the oligomer absorption maximum, an initial exciton becomes self-trapped on one of the monomer units (donors). Thereafter, an efficient ultrafast through-space energy transfer from this unit to the perylene acceptor takes place. We observe that this energy transfer occurs equally well from any monomer unit on the chain. Effective specific vibronic couplings between each monomer and the acceptor are identified. These oligomer → end-cap energy transfer steps do not match with the rates predicted by Förster-type energy transfer. The through-space and through-bond mechanisms are two distinct channels of energy transfer. The former dominates the overall process, whereas the through-bond energy transfer between indenofluorene monomer units along the oligomer backbone only makes a minor contribution.

Donor‐acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

AbstractA series of donor‐acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta‐annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2‐b:4,5‐b’]dithiophene, thieno[3,2‐b]thiophene, and 4‐octyl‐4H‐dithieno[3,2‐b:2′,3′‐d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin‐film absorption and cyclic voltammetry, of the donor‐acceptor copolymers are presented.

Efficient Light-Harvesting Antennae Resulting from the Dense Organization of Dyes into DNA Junctions through d-Threoninol.

Herein we report the construction of efficient light-harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d-threoninol. Six pyrene donors could be incorporated into each arm without self-quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three- to eight-way junctions were systematically compared. Six- and eight-way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even-numbered junctions had higher efficiencies than odd-numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd-even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems.

Efficient Light‐Harvesting Antennae Resulting from the Dense Organization of Dyes into DNA Junctions through d‐Threoninol

AbstractHerein we report the construction of efficient light‐harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d‐threoninol. Six pyrene donors could be incorporated into each arm without self‐quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three‐ to eight‐way junctions were systematically compared. Six‐ and eight‐way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even‐numbered junctions had higher efficiencies than odd‐numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems.

Interface engineering for efficient fullerene-free organic solar cells

We demonstrate the role of zinc oxide (ZnO) morphology and addition of an acceptor interlayer to achieve high efficiency fullerene-free bulk heterojunction inverted organic solar cells. Nanopatterning of the ZnO buffer layer enhances the effective light absorption in the active layer, and the insertion of a twisted perylene acceptor layer planarizes and decreases the electron extraction barrier. Along with an increase in current homogeneity, the reduced work function difference and selective transport of electrons prevent the accumulation of charges and decrease the electron-hole recombination at the interface. These factors enable an overall increase of efficiency to 4.6%, which is significant for a fullerene-free solution-processed organic solar cell.

Efficiency-Limiting Processes in Low-Bandgap Polymer:Perylene Diimide Photovoltaic Blends

The charge generation and recombination processes following photoexcitation of a low-bandgap polymer:perylene diimide photovoltaic blend are investigated by transient absorption pump–probe spectroscopy covering a dynamic range from femto- to microseconds to get insight into the efficiency-limiting photophysical processes. The photoinduced electron transfer from the polymer to the perylene acceptor takes up to several tens of picoseconds, and its efficiency is only half of that in a polymer:fullerene blend. This reduces the short-circuit current. Time-delayed collection field experiments reveal that the subsequent charge separation is strongly field-dependent, limiting the fill factor and lowering the short-circuit current in polymer:PDI devices. Upon excitation of the acceptor in the low-bandgap polymer blend, the PDI exciton undergoes charge transfer on a time scale of several tens of picoseconds. However, a significant fraction of the charges generated at the interface are quickly lost because of fast geminate recombination. This reduces the short-circuit current even further, leading to a scenario in which only around 25% of the initial photoexcitations generate free charges that can potentially contribute to the photocurrent. In summary, the key photophysical limitations of perylene diimide as an acceptor in low-bandgap polymer blends appear at the interface between the materials, with the kinetics of both charge generation and separation inhibited as compared to that of fullerenes.

Light Harvesting and Amplification of Emission of Donor Perylene–Acceptor Perylene Aggregates in Aqueous Medium

With the aid of rational design, we have synthesized a pair of water-soluble donor- and acceptor-type twisted perylene bisimide units, which together form aggregates upon lowering the pH of the medium, providing bright yellow fluorescence. The light-harvesting efficiency of the co-assembled system can be tuned by controlling the ratio of donor to acceptor and 98.1 % efficiency has been achieved.

Charge generation and transport in efficient organic bulk heterojunction solar cells with a perylene acceptor

The origin of high current density in efficient non-fullerene based bulk heterojunction (BHJ) organic solar cells employing a non-planar perylene dimer (TP) as an electron acceptor and a thiophene based donor polymer PBDTTT-CT is investigated using electrical and optical techniques. Photoluminescence measurements reveal almost complete quenching of both the donor and acceptor excitons, indicating efficient electron and hole transfer processes. The nanomorphology of the films shows fine mixing of the donor polymer and TP at 50 : 50% weight ratio with a photon to current conversion efficiency (IPCE) of 45% in the visible regime. At the donor–acceptor interface, both polymer and TP excitons undergo fast dissociation with similar time scales of a few picoseconds. The magnitude of the polaron yield of PBDTTT-CT:TP blends is observed to be comparable to that of PBDTTT-CT:PC70BM blends and exhibits similar μs-decay dynamics. A power conversion efficiency of 3.2% is achieved for devices with 50 : 50% by weight compositional ratio of polymer and TP.

Perylene–Oligothiophene–Perylene Triads for Photovoltaic Applications

AbstractA series of novel acceptor–donor–acceptor triad systems, consisting of head‐to‐tail‐coupled oligo(3‐hexylthiophene)s integrated between two terminal perylenemonoimides are described. These hybrid molecules, which differ by the length of the oligothiophene units from a quaterthiophene up to a dodecithiophene were synthesized by an effective palladium‐catalyzed Ullmann‐type homo‐coupling reaction in good yields. The optical and electrochemical properties of these compounds were determined, and on the basis of this series structure‐property relationships have been established which provide vital information for the fabrication of the corresponding photovoltaic devices. Because the synthesized perylenyl‐oligothiophenes distinguish themselves by a high absorption between 300 and 550 nm and an almost complete fluorescence quenching of the perylene acceptor, they meet the requirements for organic solar cells. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Dye-functionalized head-to-tail coupled oligo(3-hexylthiophenes)—perylene–oligothiophene dyads for photovoltaic applications

A series of novel donor-acceptor systems, consisting of head-to-tail coupled oligo(3-hexylthiophene)s covalently linked to perylenemonoimide, is described. These hybrid molecules, which differ by the length of the oligothiophene units from a monothiophene up to an octathiophene, were created via effective palladium-catalyzed Negishi and Suzuki cross-coupling reactions in good to excellent yields. The optical and electrochemical properties of these compounds were determined and based on this series structure-property relationships have been established which give vital information for the fabrication of photovoltaic devices. Because the synthesized perylenyl-oligothiophenes distinguish themselves by a high absorption between 300 and 550 nm and an almost complete fluorescence quenching of the perylene acceptor, they meet the requirements for organic solar cells.

Influence of Temperature-Induced Aggregation on Energy Transfer from a Surfactant to Micellized Perylene

Forster energy transfer from excited surfactant species was used to monitor their association with micellized perylene at different temperatures. Fluorescence from the perylene acceptor was obtained through sensitization by surfactant monomers and aggregates, the latter being identified as spectroscopic rather than physical. Surfactant monomer fluorescence was subject to a strong inner filter effect inside the micelles, indicating an abundance of spectroscopically monomeric species there. Temperature increases caused reductions in native surfactant fluorescence through thermal quenching, but sensitized fluorescence intensities generally increased with temperature. This was ascribed to a temperature-induced approach between the perylene acceptor and both monomeric and aggregated surfactant donors. Clouding of the solutions showed little evidence of organizational changes at the micellar level.

Time-resolved fluorescence of DAPI in solution and bound to polydeoxynucleotides

Fluorescence decay studies, obtained by multifrequency phase-modulation fluorometry, have been performed on DAPI in solution and complexed with natural and synthetic polydeoxynucleotides. DAPI decay at pH 7 was decomposed using two exponential components of 2.8 and 0.2 ns of lifetime values, respectively. The double exponential character of the decay was maintained over a large pH range. Phase- and modulation-resolved spectra, collected between 420 and 550 nm, have indicated at least two spectral components associated with the two lifetime values. This, plus the observation of the dependence of the emission spectrum on the excitation wavelength, suggests a lifetime heterogeneity originating from ground-state molecular conformers, partially affected by pH changes. DAPI complexed with natural polydeoxynucleotides retained most of the features of DAPI decay in solution, except for the value of the long lifetime component that was longer (approximately 4 ns) and the relative fractional fluorescence intensities of the two components that were inverted. AT polymers/DAPI complexes show single exponential decay. Solvent shielding when DAPI is bound to DNA changes the indole ring solvation and stabilizes the longer lifetime decay component. For poly(GC)/DAPI complex, the decay was similar to that of free DAPI in solution, proving the dependence on the polydeoxynucleotides sequence the different types of binding and the reliability of the fluorescence method to solve them.