School of Chemistry - Research Publications
Permanent URI for this collection
Search Results
1 - 7 of 7
-
ItemHighly Efficient Luminescent Solar Concentrators by Selective Alignment of Donor-Emitter Fluorophores(AMER CHEMICAL SOC, 2019-04-23)Vertically aligning fluorophores to the surface of a waveguide is known to be an effective approach to improve the optical quantum efficiency (OQE) of luminescent solar concentrators (LSCs). While the chromophore alignment assists waveguiding of the emitted photons to the LSC edges, it also significantly reduces the light-harvesting properties of the LSC. We report here a fluorophore pair consisting of a sphere-shaped energy donor and a rod-shaped emitter that was incorporated in LSCs to provide selective fluorophore alignment to address the reduced incident-light absorption issue. A liquid-crystal polymer matrix was used to perpendicularly align the rod-shaped acceptors to a favorable orientation for light guiding, while the sphere-shaped donor was randomly oriented to maintain its light-absorbing properties. The OQE of LSC devices with this selectively aligned donor-acceptor fluorophore system is 78% without significant loss of light-harvesting capability.
-
ItemNo Preview AvailableFluorescence anisotropy imaging of a polydiacetylene photopolymer film(CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS, 2019-06)UV-illumination of phase-separated surfactant films prepared from mixtures of photopolymerizable 10,12-pentacosadiynoic acid and perfluorotetradecanoic acid results in the formation of fluorescent polydiacetylene fibers and aggregates. In this work, the orientation of polymer strands that comprise the resulting photopolymer structures has been probed using fluorescence anisotropy imaging in combination with defocused single-molecule fluorescence imaging. Imaging experiments indicate the presence of significant fiber-to-fiber heterogeneity, as well as anisotropy within each fiber (or aggregate), with both of these properties changing as a function of film preparation conditions. This anisotropy can be attributed to various alignments of the constituent polymer strands that comprise the larger fibers and aggregates. Intriguingly, when using defocused imaging, fiber images consisted of a series of discrete “doughnut” fluorescence emission patterns, which exhibited intermittent on–off blinking behavior; both of these properties are characteristic of individual emission transition dipoles (single molecules). Further, all of the individual emission transition dipoles had a uniform orientation with respect to the axis of the fiber, indicating a common orientation of discrete emitters in the larger polymer fiber. The implications of these results for future studies of the electronic properties of conjugated polymers in larger macroscopic systems are noted.
-
ItemLiquid Crystallinity as a Self-Assembly Motif for High-Efficiency, Solution-Processed, Solid-State Singlet Fission Materials(WILEY-V C H VERLAG GMBH, 2019-08)Abstract Solution and solution‐deposited thin films of the discotic liquid crystalline electron acceptor–donor–acceptor (A‐D‐A) p‐type organic semiconductor FHBC(TDPP)2, synthesized by coupling thienyl substituted diketopyrrolopyrrole (TDPP) onto a fluorenyl substituted hexa‐peri‐hexabenzocoronene (FHBC) core, are examined by ultrafast and nanosecond transient absorption spectroscopy, and time‐resolved photoluminescence studies to examine their ability to support singlet fission (SF). Grazing incidence wide‐angle X‐ray (GIWAX) studies indicate that as‐cast thin films of FHBC(TDPP)2 are “amorphous,” while hexagonal packed discotic liquid crystalline films evolve during thermal annealing. SF in as‐cast thin films is observed with an ≈150% triplet generation yield. Thermally annealing the thin films improves SF yields up to 170%. The as‐cast thin films show no long‐range order, indicating a new class of SF material where the requirement for local order and strong near neighbor coupling has been removed. Generation of long‐lived triplets (µs) suggests that these materials may also be suitable for inclusion in organic solar cells to enhance performance.
-
ItemSolution-Processable, Solid State Donor-Acceptor Materials for Singlet Fission(WILEY-V C H VERLAG GMBH, 2018-10-25)Abstract The exploitation of singlet fission (SF) materials in optoelectronic devices is restricted by the limited number of SF materials available and developing new organic materials that undergo singlet fission is a significant challenge. Using a new strategy based on conjugating strong donor and acceptor building blocks, the small molecule (BDT(DPP)2) and polymer (p‐BDT‐DPP) systems are designed and synthesized knowing that bisthiophene‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione (DPP) has a low lying triplet energy level, which is further confirmed by time‐dependent density functional theory (TD‐DFT) calculations. TD‐DFT and natural transition orbital (NTO) analysis are conducted to gain insight into the photophysical properties and features of excited states in BDT(DPP)2, respectively. Femtosecond and nanosecond transient absorption spectroscopies are used to investigate the excited state kinetics in the synthesized compounds. Fast formation of triplet pairs in thin film of p‐BDT‐DPP and BDT(DPP)2 and the equilibrium formation of correlated triplet pairs and S1 from triplet–triplet annihilation in solution of BDT(DPP)2 are further evidence of SF in these compounds. The short triplet lifetime, as a result of fast biexcitonic recombination, provides additional support for triplet pair formation through singlet fission.
-
ItemEnergy Migration in Organic Solar Concentrators with a Molecularly Insulated Perylene Diimide(AMER CHEMICAL SOC, 2016-06-23)
-
ItemHighly Fluorescent Molecularly Insulated Perylene Diimides: Effect of Concentration on Photophysical Properties(AMER CHEMICAL SOC, 2017-10-10)
-
ItemExciton Dynamics of Photoexcited Pendant Porphyrin Polymers in Solution and in Thin Films(American Chemical Society, 2018-12-20)Several new polymers with rotatable zinc porphyrin pendants have been synthesized and their optical spectroscopic and photophysical properties, including upconversion efficiencies, determined in both fluid solution and thin films. Comparisons made with the β-substituted zinc tetraphenylporphyrin monomers and ZnTPP itself reveal that the yield of triplets resulting from either Q-band or Soret-band excitation of the polymers is surprisingly small. A detailed kinetic analysis of the fluorescence decays and transient triplet absorptions of the substituted monomers and their corresponding polymers reveals that this phenomenon is due to two parallel internal singlet quenching processes assigned to transient intrachain excimer formation. Consequently, the yields of upconverted S2 fluorescence resulting from Q-band excitation in the degassed polymers are significantly diminished in both fluid solution and thin films. Implications of these results for the design of polymer upconverting systems are discussed.