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School of Chemistry - Research Publications
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ItemHighly Efficient Luminescent Solar Concentrators by Selective Alignment of Donor-Emitter FluorophoresZhang, B ; Gao, C ; Soleimaninejad, H ; White, JM ; Smith, TA ; Jones, DJ ; Ghiggino, KP ; Wong, WWH (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.
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ItemCompetitive Triplet Formation and Recombination in Crystalline Films of Perylenediimide Derivatives: Implications for Singlet FissionMasoomi-Godarzi, S ; Hall, CR ; Zhang, B ; Gregory, MA ; White, JM ; Wong, WWH ; Ghiggino, KP ; Smith, TA ; Jones, DJ (AMER CHEMICAL SOC, 2020-05-28)Developing photostable compounds that undergo quantitative singlet fission (SF) is a key challenge. As SF necessitates electron transfer between neighboring molecules, the SF rate is highly sensitive to intermolecular coupling in the solid state. We investigate SF in thin films for a series of perylenediimide (PDI) molecules. By adding different substituents at the imide positions, the packing of the molecules in the solid state can be changed. The relationship between SF parameters and the stacked geometry in PDI films is investigated, with two-electron direct coupling found to be the main SF mechanism. Time-resolved emission and transient absorption data show that all of the PDI films undergo SF although with different rates and yields varying from 35 to 200%. The results show that PDI1 and 2, which are stacked PDI pairs twisted out of alignment along the highest occupied molecular orbital to lowest unoccupied molecular orbital transition, exhibit faster and more efficient SF up to 200% yield. We demonstrate that both triplet formation and decay rates are highly sensitive to the ordering of the molecules within a film. The results of this study will assist in the design of optimized structures with a fast SF rate and low recombination rate that are required for useful light harvesting applications.
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ItemFRET-enhanced photoluminescence of perylene diimides by combining molecular aggregation and insulationZhang, B ; Lyskov, I ; Wilson, LJ ; Sabatini, RP ; Manian, A ; Soleimaninejad, H ; White, JM ; Smith, TA ; Lakhwani, G ; Jones, DJ ; Ghiggino, KP ; Russo, SP ; Wong, WWH (Royal Society of Chemistry, 2020-07-14)The photoluminescence quantum yield (ϕPL) of perylene diimide derivatives (PDIs) is often limited by aggregation caused quenching (ACQ) at high concentration or in the neat solid-state. Energy transfer in high dye concentration systems is also a key factor in determining ϕPL as a result of energy funneling to trap sites in the sample. By tuning the substituents, we present two classes of PDIs with aggregation and insulation of the PDI core. By combining these fluorophores in a polymer film, we demonstrate highly emissive samples (85% ϕPL) at high concentration (140 mM or 20% w/w). Experimental and theoretical studies provide insight into why such a combination is necessary to achieve high ϕPL. While insulated fluorophores maintain respectable ϕPL at high concentration, an improved ϕPL can be achieved in the presence of appropriately oriented fluorophore aggregates as emissive traps. The theoretical calculations show that the relative orientation of aggregated monomers can result in energetic separation of localized states from the charge-transfer and bi-excitonic states thereby enabling high ϕPL.
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ItemNo Preview AvailableTotal Synthesis of Icumazole A Using a Modified Cadiot-Chodkiewicz CouplingBuntine, J ; Dasgupta, S ; Dorney, K ; Rubinstein, O ; Salimimarand, M ; White, JM ; Rizzacasa, MA (AMER CHEMICAL SOC, 2024-01-29)The first total synthesis of myxobacteria metabolite icumazole A (1) is reported. Key steps in the route include an organocatalyzed asymmetric self-aldol reaction followed by an acetate aldol reaction to form the stereotriad present in the oxazole moiety, an intramolecular Diels-Alder reaction to form the isochromanone, and an acetylide addition and selective methylation. The final steps involved a high-yielding modified Cadiot-Chodkiewicz coupling and stereoselective reduction to secure the Z,Z-diene and afford 1.
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ItemNo Preview AvailableCooperative assemblies featuring hydrogen bonding and C-H...π interactions in 2-(methanesulfonamido)benzohydrazide derivatives: Experimental, computational and biochemical assessmentMunir, R ; Zaib, S ; Khan, I ; Yousaf, A ; McAdam, CJ ; White, JM ; Hokelek, T ; Awwad, NS ; Ibrahium, HA ; Frontera, A (ELSEVIER, 2024-01-05)
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ItemSemisynthesis and Cytotoxic Evaluation of an Ether Analogue Library Based on a Polyhalogenated Diphenyl Ether Scaffold Isolated from a Lamellodysidea SpongeRamage, KS ; Lock, A ; White, JM ; Ekins, MG ; Kiefel, MJ ; Avery, VM ; Davis, RA (MDPI AG, 2024)The known oxygenated polyhalogenated diphenyl ether, 2-(2′,4′-dibromophenoxy)-3,5-dibromophenol (1), with previously reported activity in multiple cytotoxicity assays was isolated from the sponge Lamellodysidea sp. and proved to be an amenable scaffold for semisynthetic library generation. The phenol group of 1 was targeted to generate 12 ether analogues in low-to-excellent yields, and the new library was fully characterized by NMR, UV, and MS analyses. The chemical structures for 2, 8, and 9 were additionally determined via single-crystal X-ray diffraction analysis. All natural and semisynthetic compounds were evaluated for their ability to inhibit the growth of DU145, LNCaP, MCF-7, and MDA-MB-231 cancer cell lines. Compound 3 was shown to have near-equivalent activity compared to scaffold 1 in two in vitro assays, and the activity of the compounds with an additional benzyl ring appeared to be reliant on the presence and position of additional halogens.
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ItemNo Preview AvailableA cis-β-iron(iii) SALPN catalyst for hydrogen atom transfer reductions and olefin cross couplingsRicca, M ; Yao, S ; Le, T ; White, JM ; Donnelly, PS ; Rizzacasa, MA (ROYAL SOC CHEMISTRY, 2023-08-23)An inexpensive Fe(III) SALPN catalyst for MHAT reactions such as reductions of α,β-unsaturated carbonyl compounds and olefin cross couplings is reported. The majority of these reactions proceeded in good yields and high stereoselectivities with low catalyst loadings at room temperature.
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ItemNo Preview AvailableSynthesis of More Highly Oxidized Alkyl Citrates via Direct Regio- and Stereoselective OxidationRossouw, NP ; Chen, Z ; White, JM ; Rizzacasa, MA (AMER CHEMICAL SOC, 2023-11-02)An approach to more highly oxidized alkyl citrates by direct regio- and stereoselective oxidations is reported. The total synthesis and structural assignment of alkyl citrate L-731-128 are described, and the synthesis of its C4 oxidized congener L-731,127 utilized a regio- and stereoselective enolate oxidation with oxygen gas. A highly stereoselective Rubottom oxidation of a cyclic silylketene acetal then enabled oxidation at C2 to afford the cinatrins C1 and C3.
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ItemNo Preview AvailableHammett Structural Relationships Revealed in Chalcogen-Bonded Co-Crystals of Electron-Rich Pyridines with 4′-Substituted Ebselen DerivativesFellowes, T ; Lee, E ; Tran, J ; Xu, R ; Barber, A ; Brydon, SC ; Clegg, JK ; White, JM (AMER CHEMICAL SOC, 2023-08-30)
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ItemNo Preview AvailableMono and binuclear cadmium complexes: X-ray crystal structures, Hirshfeld surface analysis and antimicrobial/antioxidant studiesAkbari, Z ; Montazerozohori, M ; Joohari, S ; Hayati, P ; Micale, N ; Cristani, M ; Bruno, G ; White, JM (Elsevier BV, 2023-12-01)