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A series of poly(phenylene-vinylene)-based copolymers are synthesized using the Gilch method incorporating monomers with sterically bulky sidechains. The photochemical upconversion performance of these polymers as emitters are investigated using a palladium tetraphenyltetrabenzoporphyrin triplet sensitizer and MEH-PPV as reference. Increased incorporation of sterically bulky monomers leads to a reduction in the upconversion efficiency despite improved photoluminescence quantum yield. A phosphorescence quenching study indicates issues with the energy transfer process between the triplet sensitizer and the copolymers. The best performance with 0.18% upconversion quantum yield is obtained for the copolymer containing 10% monomer with bulky sidechains.

A series of poly(phenylene-vinylene)s (PPV) was synthesized with two monomer building blocks containing methoxy and 2-ethylhexyloxy (MEH) sidechains and sterically bulky fluorenyloxy sidechains. Variations in monomer incorporation were achieved by adjusting the ratio of the monomer precursors in the synthesis of the PPVs using the Gilch polymerization method. The increased incorporation of the bulky monomer led to expected variation in photophysical properties, in particular, the enhancement of photoluminescence quantum yield. Using palladium(II) tetraphenyltetrabenzoporphyrin (PdTPTBP) as the triplet sensitizer, all polymers displayed upconverted emission in solution with the comonomer ratio for the fluorenyloxy and MEH units at 1 : 10 showing the best performance with upconversion efficiency of 0.135%. This efficiency was up to three times higher than that of two commercially available PPVs, MEH-PPV and Super yellow PPV, under the same experimental conditions. Further analysis of the efficiency of the photochemical processes involved revealed several limitations to the performance of these conjugated polymer emitters. While increasing steric bulk of the sidechains improved the photoluminescence quantum yield, it also caused variation in excited state energies of the polymers through the series. This led to poor alignment with the triplet energy of our chosen sensitizer for some of the polymers. Even when the triplet–triplet energy transfer efficiency was high, the contact triplet pair formation efficiency was found to be very low. We reasoned that the structural conformation of the polymers hindered the chromophore orbital overlap during triplet collisions required for triplet–triplet annihilation.

Developing photostable compounds that undergo quantitative SF is a key challenge. As singlet fission necessitates electron transfer between neighboring molecules, the SF rate is highly sensitive to...

Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination-poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains-away from the interface-resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.

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.

A high-performance large-area luminescent solar concentrator (LSC) is demonstrated, fabricated via careful choice of the fluorophore system, waveguide material, and coupled photovoltaic (PV) cells....

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.

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.

Diketopyrrolopyrrole (DPP) derivatives have been proposed for both singlet fission and energy upconversion as they meet the energetic requirements and exhibit superior photostability compared to many other chromophores. In this study, both time-resolved electronic and IR spectroscopy have been applied to investigate excited state relaxation processes competing with fission in dimers of DPP derivatives with varying linker structures. A charge-separated (CS) state is shown to be an important intermediate with dynamics that are both solvent and linker dependent. The CS state is found for a subset of the total population of excited molecules and it is proposed that CS state formation requires suitably aligned dimers within a broader distribution of conformations available in solution. No long-lived triplet signatures indicative of singlet fission were detected, with the CS state likely acting as an alternative relaxation pathway for the excitation energy. This study provides insight into the role of molecular conformation in determining excited state relaxation pathways in DPP dimer systems.

A zinc porphyrin-pendant norbornene polymer with a rigid backbone characterized by a 2:1 E/Z isomeric structure ratio has been synthesized, and its spectroscopic and photophysical properties are examined. Zinc tetraphenylporphyrin, the porphyrin-substituted norbornene monomer, and a previously reported zinc porphyrin-pendant polymer with a flexible polymethylene backbone have been used as comparators. Unlike its flexible counterpart, the rigid norbornene polymer exhibits clear exciton splitting of its Soret band, much more rapid relaxation rates of its excited singlet states, and a very small yield of an unusually short-lived triplet state. Unlike the flexible pendant polymer, which exhibits excimeric S2 fluorescence as a result of chromophore rotation, anti-Kasha emission from the norbornene polymer originates primarily from the unperturbed porphyrin E region. The low triplet yield in the polymer is attributed to greatly increased rates of competing internal conversion within the singlet manifold. Nevertheless, upconverted delayed fluorescence that is quenched by oxygen is observed upon intense steady-state Q-band excitation of degassed polymer solutions, signaling direct triplet involvement. Consistent with the polymer's rigid structure, this biexcitonic process is assigned to ultrafast singlet exciton migration and triplet-triplet annihilation following absorption of a second photon by the small steady-state concentration of polymer triplets.

Summary The realization of robust luminescence in crystalline and anisotropic nanowires of wide bandgap light-emitting conjugated polymers (LCPs) is challenging. Compared to the periodic arrangements in conventional crystalline nanostructure, hierarchical uniform structures will provide an electronic landscape to obtain excellent optoelectronic behaviors, which are desirable for polymer light-emitting diodes (PLEDs) and polymer lasers. Here, we construct a range of robust hierarchical uniform crystalline nanowires of wide bandgap polydiarylfluorenes for light-emitting optoelectronic applications. Steric hindrance interactions of the bulky groups enable these nanowires to show a robust deep-blue emission, due to the suppression of interchain aggregation. Therefore, efficient deep-blue nanowire-based PLEDs with an intrachain excitonic behavior are fabricated. Moreover, our β-conformational hierarchical uniform nanowires present a low-threshold deep-blue lasing behavior. To the best of our knowledge, this is the first deep-blue organic nanolaser based on LCPs self-assembled nanowires by constructing hierarchical uniform crystalline structure.

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.

The electronic spectroscopy and photophysics of 1,2-benzazulene (BzAz) have been examined in solution and in thin solid films, with the objective of comparing its intramolecular and intermolecular excited state decay processes with those of azulene. Unlike azulene, the S2 – S0 absorption and fluorescence spectra exhibit a clear mirror image relationship dominated by a single strong Franck-Condon active progression. Picosecond transient absorption spectra and non-linear S2 fluorescence upconversion experiments reveal lifetimes that follow a well-established energy gap law correlation, indicative of a dominant S2 – S1 decay route. Mechanistic interpretations, including the possibility of S2 singlet fission in aggregates, are discussed.

A facile method is proposed to obtain modified shorn graphene oxide (DDAB-sGO) with improved dispersion in organic solvents. Didodecyl dimethylammonium bromide (DDAB)-sGO, which exhibits good dispersibility in the nonpolar solvent o-dichlorobenzene, was obtained via the sono-Fenton reaction and DDAB ionic functionalization. DDAB-sGO was used in the preparation of conjugated polymer:fullerene blend composites. UV–visible absorption spectra, steady-state photoluminescence spectra, fluorescence decay, and grazing incidence X-ray scattering measurements were applied to characterize morphologies, structural features, and charge-transport characteristics of the composites. Doped into poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7):[6,6]-phenyl C71 butyric acid methyl ester (PC71BM) conjugated polymer blends, DDAB-sGO is shown to facilitate increased crystallinity and phase separation of PTB7 and PC71BM to achieve a m...

Perovskite microplates have important implications in the fields of functional electronics and optoelectronics. We report a facile strategy, antisolvent treatment for the growth of perovskite microplates. The morphology and crystalline quality of the microplates could be controlled by the amount of the chlorobenzene antisolvent used. An appropriate amount of antisolvent facilitates the formation of high-quality perovskite microplates with no residual precursor remaining. Spatially and temporally resolved fluorescence measurements demonstrate the heterogeneity of defect-state density and recombination processes in various perovskite microplate regions. The body center shows higher defect state density when compared with that at the edge or the corner of the microplate. Excessive antisolvent degrades the microplates into smaller particles. The results of this study reveal the factors that influence the crystallization process and photophysical dynamics of perovskite microplates.

A series of four perylene diimide (PDI) chromophores were prepared with increasing steric bulk on the imide substituents with the aim of retarding the effect of concentration quenching on photoluminescence, commonly observed with these dyes. Spectroscopic investigations of the compounds in dilute solution confirmed that the photophysical properties of the PDI core chromophore were not perturbed by the bulky substituents. Solid film samples containing the PDI compounds at various concentrations dispersed in a poly(methyl methacrylate) (PMMA) matrix were examined and compared to amorphous neat films as well as crystalline samples. The PDI compounds containing di-tert-butylphenyl (bPDI-3) and trityl (bPDI-4) substituents showed near unity photoluminescence quantum yield (PLQY) up to 20 mM in PMMA compared to 10% PLQY for the reference compound (bPDI-1) without molecular insulation. Surprisingly, high concentrations (>40 mM) of a phenyl-substituted PDI compound (bPDI-2) with moderate molecular insulation form...

An effective method for preparing poly(3-hexylthiophene) (P3HT) coated graphene oxide (GO), (P-GO), based on an ethanol mediated mixing and solvent evaporation method is described. P-GO exhibits good dispersibility in the non-polar solvent o-dichlorobenzene (DCB) allowing the preparation of polymer blend composites. P-GO was doped into P3HT: PCBM blends by solution mixing and shown to facilitate phase separation of P3HT and PCBM in P3HT: PCBM blend films to achieve a more optimum morphology for polymer photovoltaic cells. Bulk heterojunction P3HT: PCBM solar cells exhibit ∼18% power conversion efficiency enhancement in the presence of P-GO.

2-Chlorophenyl isocyanate (CI) reacts with didodecyl dimethyl ammonium bromide (DDAB) functionalized graphene oxide (DDAB-GO) dispersed in ortho-dichlorobenzene under mild conditions. The CI treatment complements DDAB functionalization to further decrease the hydrophilicity of pristine GO sheets. The resulting CI–DDAB-GO exhibits improved compatibility with the conjugated polymer poly(3-hexylthiophene) (P3HT), compared to DDAB-GO. CI–DDAB-GO sheets can be homogeneously dispersed when blended with P3HT, resulting in an improved morphology compared to P3HT:DDAB-GO composites. The incorporation of CI–DDAB-GO can effectively reduce the dark current of photo-diodes based on P3HT composites, showing potential to enhance the performance of electronic devices based on conjugated polymer composites.

Spectroscopic, photophysical and computational studies designed to expose and explain the differences in the efficiencies of non-coherent photon upconversion (NCPU) by triplet-triplet annihilation (TTA) have been carried out for a new series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins, both in fluid solution and in solid films. Systematic variations in the alkyl-substitution of the phenyl groups in both the di- and tetraphenyl porphyrins introduces small, but well-understood changes in their spectroscopic and photophysical properties and in their TTA efficiencies. In degassed toluene solution TTA occurs for all derivatives and produces the fluorescent S2 product states in all cases. In PVA matrices, however, none of the di-phenylporphyrins exhibit measurable NCPU whereas all the tetraphenyl-substituted compounds remain upconversion-active. In PVA the NCPU efficiencies of the zinc tetraphenylporphyrins vary significantly with their steric characteristics; the most sterically crowded tetraphenyl derivative exhibits the greatest efficiency. DFT-D computations have been undertaken and help reveal the sources of these differences.

Nanoscale morphology and spin can have a significant impact on charge generation and short time scale recombination in organic photovoltaic materials. We reveal multiple efficient charge separation pathways and the suppression of triplet loss channels in a high-performing nematic liquid crystalline electron donor, benzodithiophene terthiophene rhodanine (BTR). BTR:PC71BM bulk heterojunction photovoltaic devices have been shown to exhibit charge generation quantum yields of ∼90% and power conversion efficiencies >9.5%, even in thick devices. Solvent vapor annealing increases device efficiency, delivering performance almost twice as high as that of untreated blend films, despite reduced exciton quenching. Broadband femtosecond transient absorption spectroscopy reveals both efficient hole and electron transfer on different time scales in the bulk heterojunction blends. BTR triplet excitons are formed due to subnanosecond bimolecular recombination in untreated blend films, though their formation is significan...

Maintaining high incident light absorption while minimizing luminescence reabsorption is a key challenge for organic luminescent solar concentrators (LSCs). Energy migration and trapping using light-harvesting donors and a low-energy highly emitting acceptor is one strategy to reduce the reabsorption issue. However, concentration quenching and the potential formation of quenching aggregates is a limiting factor in realizing efficient devices. We describe the synthesis of a novel molecularly insulated perylene diimide that can resist luminescence quenching at concentrations in excess of 50 mM. Photophysical measurements show the insulated perylene diimide has an excitation energy migration diffusion length of 230 ± 10 A at 60 mM in poly(methyl methacrylate). LSC devices using a mixture of the insulated perylene diimide light absorber and perylene red (LR305) as the low-energy trap emitter exhibit reduced reabsorption and a better current output than LR305 only devices. The results demonstrate that appropri...

We report the effect of the processing solvent on the nanoscale morphology and photophysical dynamics of poly(3-butyl-thiophene) nanowires (P3BT-nw). P3BT-nw assembled in ortho-dichlorobenzene (ODCB) show higher crystallization and a longer conjugation length with increased exciton delocalization compared with those assembled in chlorobenzene (CB). It is proposed that this solvent effect is associated with the higher ordered structures formed from ODCB solution state. Charge-transfer dynamics and phase separation for P3BT-nw:PCBM blends were investigated by ultrafast fluorescence techniques. The more efficient fluorescence quenching observed in P3BT-nw:PCBM blend films processed from ODCB suggests that there is intimate contact between P3BT-nw and PCBM that facilitates charge transfer. The superior performance of organic photovoltaic devices based on P3BT-nw:PCBM bulk heterojunctions processed using ODCB is attributed to the higher crystallization of P3BT-nw, optimized phase separation, and more efficient charge transfer from P3BT-nw to PCBM.

Calix[4]azulene is a non-alternant aromatic calixarene composed of four azulene chromophores linked by methylene groups. Its photochemical stability, photophysical properties and an analysis of its electronic spectra are reported using monomeric azulene as a known reference standard. The molecule is stable when excited in its visible and near uv absorptions and, unlike azulene, produces no measurable “anti-Kasha” fluorescence when excited to its second excited singlet state, S2. This lack of fluorescence places the lifetime of the initially excited, photochemically stable S2 species at less than 1 picosecond. A significant, bathochromic shift of the S2 absorption band system in the calixarene, and the appearance of an additional weak, broad absorption immediately to the red signals significant intramolecular chromophore interaction. Femtosecond transient absorption spectroscopy using excitation in this red-shifted tail of the S2 band system reveals a very weak transient signal most of which decays within one ps, but with suggestions of a slightly longer-lived underlying component. No longer-lived T1 triplet transient is observed. A complete analysis of the data using monomeric azulene as a reference suggests, following elimination of several alternate mechanisms, that the initially excited S2 species may be relaxing via a novel singlet-singlet fission process.

We report the observation of singlet fission in aqueous suspensions of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn) nanoparticles (NPs) synthesized using the reprecipitation method. By altering the synthesis conditions we are able to fabricate NPs which evolve from a system of poorly coupled to highly coupled chromophores. This morphological evolution can also be suppressed for a period of several months. Absorption spectra confirm that the particles evolve over time, displaying increased intermolecular interaction, if the initial reaction conditions seeded a polycrystalline sample. We correlate these differences in morphologies to different rates of singlet state decay, where higher intermolecular interaction drives a more rapid rate of decay. Ultrafast time-resolved photoluminescence spectroscopy confirms a short first excited singlet state lifetime (

The successful synthesis is described for a donor–acceptor rod–coil block copolymer comprising blocks of poly[2,7-(9,9-dihexylfluorene)-alt-bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C60)) (F6T2-b-PS(C60)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2-b-PS(C60)) and a related block copolymer (F6T2-b-PS(PCBM)) (PCBM, phenyl-C61-butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod–coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 888–903

Kunal Dhoke, Martin Zanni, Upendra Harbola, Ravi Kumar Venkatraman, Elangannan Arunan, King-Chuen Lin, Artur Nenov, Jonathan Skelton, R J Dwayne Miller, Jonathan D. Hirst, Vincenzo Aquilanti, John R. Helliwell, Srihari Keshavamurthy, Sai Ramesh, Mike Ashfold, Anuradha Pallipurath, Priyadarshi Roy Chowdhury, Sanghamitra Mukhopadhyay, Jemmis E D, Himani Medhi, Debabrata Goswami, Prasenjit Halder, Wolfgang Junge, Mahesh Hariharan, Santosh Kumar Singh, Siva Umapathy, Adithya Lakshmannam, Martin Meedom Nielsen, Sankarampadi Aravamudhan, Volker Deckert, Kenneth Ghiggino, Keisuke Tominaga and Alison Edwards

The energy levels of graphene oxide (GO) and reduced graphene oxide (rGO) were estimated in this work. We demonstrate that the energies of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) of GO become closer to each other upon reduction. GO and rGO were blended with poly(3-hexylthiophene) (P3HT) to form composite films and their optoelectronic properties were evaluated. It was found that both electrons and holes from photoexcited P3HT can transfer to rGO leading mostly to recombination while only electrons transfer to GO.

Non-coherent photon upconversion by rapid intramolecular triplet–triplet annihilation has been observed following nanosecond laser excitation of Ru(dmb) 3 and sequential two-fold triplet energy sensitization of a polymer containing 30 pendant diphenylanthracene groups. A global kinetic analysis of the system has been performed; the intramolecular annihilation step occurs on a sub-nanosecond time scale.

Time-resolved fluorescence anisotropy measurements (TRAMs) are widely used to probe the dynamics of the various processes that can lead to the depolarisation of emission following photoselection by polarised excitation. The most commonly investigated of these emission depolarising phenomena is molecular rotational motion, but TRAMs are very useful for determining the kinetics of a host of other processes. In this paper we review several examples for which we have observed in our laboratories initially unexpectedly complex temporal behaviour of the time-resolved fluorescence anisotropy signal from relatively 'simple' chemical systems. In certain circumstances the anisotropy (i) decays on timescales when superficially it might be thought it should remain constant, (ii) shows marked 'dip and rise' behaviour in its intensity, or (iii) can change sign as the anisotropy evolves in time. Fundamentally simple processes, including molecular rotational motion, energy migration and excited state photophysics, can cause such behaviour.

The photophysics of a conjugated triblock copolymer comprising poly(9,9-dioctylfluorene-co-bis-N,N'-(4-methylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine) (PFM) electron donor and poly(4-(9,9-dioctyl-9H-fluoren-2-yl)benzo[c][1,2,5]-thiadiazole) (F8BT) electron acceptor blocks has been studied in solution, in films, and as single chains. While an additional long-wavelength emission apparent in neat films of the copolymer is attributed to interchain exciplex formation, no such long-wavelength emission is apparent in solution or from single molecules. However, in these cases, time-resolved fluorescence measurements indicate the presence of a delayed fluorescence. The kinetics of the delayed emission can be interpreted in terms of an equilibrium between a locally excited and a charge-transfer state at the interface of the copolymer block components. Rate constants and thermodynamic quantities associated with these processes have been evaluated. The single-molecule results allow the assignment of an intramolecular charge-transfer state in an isolated conjugated block copolymer chain.

Two photophysically active polymers, each containing one absorbing Ru(bpy)3 triplet sensitizing core and multiple 9,10-diphenylanthracene (DPA) triplet energy acceptors, are shown to exhibit noncoherent photon upconversion by triplet–triplet annihilation (TTA) in both fluid solution and in thin solid films. An analysis of the kinetics and absorbed power dependencies of the upconverted fluorescence demonstrates that, in fluid solution, TTA is occurring in the low-power, pseudo-first order limit, and that the energy transfer mechanism involves fast, efficient intramolecular triplet energy transfer from the excited Ru(bpy)3 core to the DPA acceptors in the macromolecule’s pendant arms, followed by intermolecular TTA. Intermolecular triplet energy transfer, diffusion coefficient, and quantum yield measurements using Ru(bpy)3 and DPA controls suggest that, although a minority of the intermolecular encounters result in TTA in this one absorbing core system, efficient intramolecular TTA could be realized in a po...

Triplet and singlet excitation energy transfer processes are investigated in two novel di- and hexa-functionalised ruthenium centred polymers prepared by RAFT methods. The polymers consist of a ruthenium trisbipyridyl ligand complex (Ru(bpy) 3 ) core and pendant polymer ‘arms’ of 9,10-diphenylanthracene (DPA). Steady state and transient emission and absorption experiments are used to investigate intramolecular energy transfer processes following photoexcitation of Ru(bpy) 3 and DPA. Triplet energy transfer from the Ru(bpy) 3 core to pendant DPA chromophores in the polymer arms is found to be more efficient than the reverse singlet energy transfer process, attributed in part to the long triplet lifetime of Ru(bpy) 3 and the polymer structure. A consequence is that intra-polymer chain triplet energy transfer from Ru(bpy) 3 to DPA chromophores followed by triplet–triplet annihilation and delayed fluorescence from the DPA can be observed.

A series of solution processable conjugated polymers containing the benzotriazole unit have been synthesized and studied. The benzotriazole unit can be considered a moderately electron deficient building block that can readily incorporate a convenient alkyl substituent for solution processability. By varying the electron accepting strength of co-monomer partners, a series of polymers with different photophysical properties were obtained. Some polymers exhibit relatively high fluorescence quantum yields while others were able to quench the fluorescence of electron donor polymers in blends consistent with their ability to act as electron acceptors. The performance of these polymers as the active material in organic light emitting diode (OLED) and organic photovoltaic (OPV) devices is reported.

The fluorescence spectra, quantum yields and lifetimes of a series of alkoxy-substituted phenylenevinylene molecules, which serve as short chain oligomer models for poly(p-phenylenevinylene), have been determined in fluid solvents and in a high viscosity polymer matrix. The effects of solvent polarity and a high viscosity molecular environment on the fluorescence yields and spectral shapes have been established. Alkoxy group substitution on the phenyl ring moieties of the molecules has an important effect on the vibronic structures and profiles of the absorption spectra. This was interpreted in terms of hot-band, ground to excited singlet state transitions from energetically closely-spaced torsional vibrational levels of the vinylene double bond in the ground state. The shapes of the absorption bands affect the overlaps of the absorption and fluorescence spectra. This has been quantified as the probability of fluorescence reabsorption in solid polymer films as a function of pathlength. This is an important determinant of the efficacies of these compounds for “harvesting” solar energy in luminescent solar concentrator systems. The reabsorption probabilities of these compounds are lower for all pathlengths than those determined in the same polymer film for the fluorophores, perylene and perylene diimide, which have been considered for concentrating spatially diffuse sunlight.

The effect of dye concentration on the efficiency of a luminescent concentrator based on a perylene diimide (PDI) derivative incorporated in poly(methyl methacrylate) films cast on glass substrates is described. The predictions of ray-trace modelling are compared to experimental data from integrating sphere luminescence measurements. Increasing the PDI concentration leads to aggregation of the dye and an associated shift in the emission spectrum. The larger Stokes shift between emission and absorption spectra of the aggregated form reduces luminescence re-absorption and increases collection efficiency. However, the lower fluorescence quantum yield of the PDI aggregates restricts overall absorbed light to luminescence conversion. The relevance of the results to optimize organic molecule based luminescent solar concentrators is discussed.

Synthetic polymers incorporating appropriate chromophores can act as light harvesting antennae for artificial photosynthetic systems. The photophysical processes occurring in a polymer based on phenylene vinylene have been investigated at the single chain level and in bulk solution to study energy transfer processes. Most single chains of an alternating copolymer of 2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene and 1,4-phenylene vinylene (alt-co-MEH-PPV) dispersed in a transparent polymer matrix act as single chromophore emitters demonstrating that energy transfer is an efficient process in these polymers. However for individual polymer chains there are fluctuations in emission intensity ('blinking') and shifts in emission spectra, decay lifetimes and emission dipole orientation occurring on a time-scale of tens of seconds. Fluorescence blinking also occurs on a sub-millisecond time-scale and follows exponential kinetics, whereas the longer blinking is better described by a power law. These observations can be interpreted as arising from environmental relaxation processes and/or changes in the emitter and demonstrate the wide distribution of photophysical behaviours that can be observed among the individual molecules of a polymer sample. The relevance of these studies to the application of polymer materials for solar harvesting is highlighted.

The potential for iron(III) tartrate to act as a photoactivator in light-induced oxidative degradation of white wine is described. Using a tartaric-acid-based model wine system containing 5 mg/L iron, exposure to light from a xenon arc lamp led to the oxidative degradation of tartaric acid and the production of glyoxylic acid. The critical wavelength of light for the degradation process was found to be below 520 nm. No glyoxylic acid was formed in the absence of iron and/or light. Flint glass offered little protection from the light-induced photodegradation of tartaric acid. Antique Green glass offered more protection but did not stop the photodegradation process.

The aggregation of metalloporphyrins is believed to play a crucial role in the excited-state annihilation process known as triplet–triplet annihilation, which in turn has significant potential applications in photon upconversion schemes. In this work, the propensity of the water-soluble metalloporphyrin zinc (II) meso-tetra(4-sulfonatophenyl)porphine to undergo aggregation when adsorbed to glass cover slips was investigated by single-molecule fluorescence microscopy. In proof-of-principle experiments, it was demonstrated (1) that individual molecules of the metalloporphyrin can be directly visualized in spite of their very weak fluorescence emission, and (2) that at low concentrations (10−8 mol/L), the molecule has a strong tendency to form multimolecular aggregates. A subset of the multimolecular aggregates shows a significant blue-shift in fluorescence emission, though at present the precise nature of the molecular aggregates remains unclear.

The synthesis and photophysics of two new aminopropenyl naphthalene diimide (SANDI) dyes are reported. A general and convenient method for the synthesis of the precursor mono-, di-, and tetrabrominated 1,4,5,8-naphthalene tetracarboxylic dianhydrides is described. The two core-substituted SANDIs exhibit many of the photophysical properties required for fluorescence labeling applications including high photostability and high fluorescence quantum yields (>0.5) in the visible region of the spectrum. The emission wavelength is sensitive to the number of substituents on the NDI core, and the fluorescence decay times are in the range of approximately 8-12 ns for both compounds in the solvents investigated. Preliminary fluorescence emission data from single molecules of the compounds embedded in poly(methyl methacrylate) films are also reported and show that single molecules have very low yields of photobleaching, particularly the di-substituted system. Furthermore, only a small proportion (

We demonstrate that the binding of N-donor ligands (4-picoline, imidazole) or anions (chloride) to the terminal zinc(II) porphyrin of selectively metalated triad and tetrad porphyrin arrays allows ...

The synthesis of easily functionalized and highly soluble fluorene-containing hexabenzocoronenes (FHBC) has been achieved in high yield at a gram scale. Conjugated triarylamine oligomers were coupled to the FHBC cores via Buchwald-Hartwig coupling, and the photophysical properties of resulting dendritic materials were examined by ultrafast laser spectroscopic techniques. Efficient quenching of the triarylamine oligomer fluorescence was observed paving the way for the inclusion of these materials in bulk heterojunction solar cells. In preliminary studies, solar cell devices with external quantum efficiencies above 5% have been fabricated.

Intramolecular photoinduced electron transfer (PET) processes occurring in dyads with a free base porphyrin-tetraazaanthracene donor (P) and either a tetracyanonaphthoquinidodimethane (TCQ) or benzoquinone (BQ) acceptor linked by a rigid six σ-bond polynorbornane bridge ([6]) have been investigated. For P[6]BQ , PET in the polar solvent benzonitrile ( ɛ s = 25.9) occurs with a rate constant ( k PET ) of 1.6 × 10 8 s −1 but is not evident in solvents less polar than tetrahydrofuran ( ɛ s = 7.52). For P[6]TCQ , highly efficient forward PET occurs in both polar and non-polar solvents ( k PET > 2 × 10 10 s −1 ). For P[6]TCQ the lifetime of the resulting charge-separated state decreases markedly with increasing solvent polarity. The results are discussed in the context of the likely mechanisms for electronic coupling and current theories for PET processes in such linked molecular systems.

The spectroscopic and photophysical properties of a typical dithiobenzoate reversible addition-fragmentation chain transfer (RAFT) polymerization agent alone in solution, as a quencher of electronically excited acenaphthene in solution, and in an acenaphthene donor-dithiobenzoate acceptor dichromophore have been investigated. The RAFT agent is an effective quencher of photo-excited acenaphthene. Energy wastage in the dichromophore occurs by Förster resonant electronic energy transfer from the S1 state of acenaphthene to the S2 state of the dithioester, which subsequently fragments.

The synthesis of a Zn (II) porphyrin-fullerene dyad in which the two chromophore units are tethered by a conformationally-flexible linker, is described. The synthesis is highlighted by the use of a cross metathesis strategy to prepare the linker between the chromophores. Photoexcitation of the Zn (II) porphyrin unit of the dyad in tetrahydrofuran leads to substantial (77%) quenching of porphyrin fluorescence. The multiple exponentials fluorescence decay kinetics observed are attributed to different rates of electron transfer from photoexcited porphyrin to fullerene in the various conformers present. A charge-separated state with a 330 ns lifetime is observed by transient spectroscopy.

A comprehensive study of the photophysical properties of chlorophyll (Chl) d in 1:40 acetonitrile-methanol solution is performed over the temperature range 170-295 K. From comparison of absorption and emission spectra, time-dependent density-functional calculations and homologies with those of Chl a, we assign the key features of the absorption and fluorescence spectra. Possible photophysical energy relaxation mechanisms are summarized, and thermal equilibration processes are studied in detail by monitoring the observed emission profiles and quantum yields as a function of excitation energy. In particular, we concentrate on emission subsequent to excitation in the extreme far-red tail of the Qy absorption spectrum, with this emission partitioned into contributions from hot-band absorptions as well as uphill energy transfer processes that occur subsequent to absorption. No unusual photophysical processes are detected for Chl d; it appears that all intramolecular relaxation processes reach thermal equilibration on shorter timescales than the fluorescence lifetime even at 170 K. The results from these studies are used to reinterpret a previous study of photochemical processes observed in intact cells and their acetone extracts of the photosynthetic system of Acaryochloris marina. In the study of Mimuro et al., light absorbed by Chl d at 736 nm is found to give rise to emission by another species, believed to also be Chl d, at 703 nm; this uphill energy transfer process is easily rationalized in terms of the thermal equilibration processes that we deduced for Chl d. However, no evidence is found in the experimental results of Mimuro et al. to support claims that (nonequilibrium) uphill energy transfer is additionally observed to Chl a species that emit at 670-680 nm. This finding is relevant to broader issues concerning the nature of the special pair in photosystem II of A. marina because suggestions that it is comprised of Chl a can only be correct if nonthermal uphill energy transfer processes from Chl d are operative.

The synthesis and structural characterisation of a series of cobalt complexes of 1-(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane (hereafter L2) is described. The complexes, of the type trans-[CoL2X2]+ in which X = Cl−, NCS− and NO 2 - were synthesised for their use in photoactivated ligand release studies. X-ray crystal structures show that the macrocycle in all three complexes of the series adopts a trans-(III) configuration. Both thiocyanato ligands were found to be N-bound in trans-[CoL2(NCS)2]+ while trans-[CoL2(NO2)2]+ contained both a nitro and nitrito ligand in the one complex. The synthesis of the complex cis-[CoL2(NO2)2]+ from sodium hexanitrocobaltate(III) is also described. This complex also contains both a nitro and nitrito ligand in the one complex, with the cyclam in a cis-(V) arrangement about the metal centre.

The synthesis, characterization, and photophysical properties of a series of supramolecular triads consisting of a tin(IV) porphyrin with axial ligands of ortho-, meta-, and para-hydroxyphenyl naphthalenediimides are presented. For the meta- and parahydroxyphenyl derivatives, efficient and solvent-viscosity- dependent quenching of porphyrin fluorescence is observed. Experimental and theoretical studies demonstrate that, in these compounds, photoinduced electron transfer from the phenolate to the porphyrin is modulated by large amplitude rotational motions of the naphthalenediimide. These compounds are novel examples of fluorescent molecular rotors, and their potential use as environmental probes of local viscosity and temperature are discussed. © 2007 WILEY-VCH Verlag GmbH &. Co. KGaA.

The fluorescence decay kinetics from a benzonitrile solution of a dibenzo-18-crown-6 ether bridged porphyrin-fullerene dyad has been studied in the presence of a range of metal ions. Dual-exponential fluorescence decay behaviour has been attributed to conformational flexibility of the molecule influencing quenching interactions between the photo-excited porphyrin and fullerene. Additions of sodium, potassium and lithium ions significantly modulate the observed fluorescence decay processes while the larger tetrabutylammonium ion has only a minor affect. The results are discussed in terms of ion inclusion within the crown ether affecting both the bridge conformational properties and donor-acceptor electronic interactions.

Reversible addition-fragmentation chain transfer (RAFT) polymerization has been used to synthesize a star-shaped light-harvesting polymer comprising six diblock copolymer arms of styryl coumarin (St-Coumarin) and methyl acrylate (MA) surrounding a ruthenium (II) trisbipyridyl energy trap core. The efficiency of excitation energy transfer from the styryl coumarin units to the Ru(II) core is increased to 90% compared to 60% for the analogous star polymer without MA blocks. The enhanced excitation energy transfer efficiency arises from the role of the MA blocks in diminishing the competitive quenching of photoexcited St-coumarin chromophores by dithiobenzoyl polymer end groups present from the RAFT polymerization procedure.