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The efficient conversion of low-energy, near-infrared (NIR) photons to higher energies promises advancements across a range of disparate fields, from more efficient solar energy capture to advanced biologic studies and therapies. At the forefront of this effort, upconverting nanoparticles (UCNPs) contain an array of lanthanide ions alloyed into a ceramic matrix, most commonly NaYF4. These lanthanide ions possess a 4f orbital manifold with a series of ladder-like, long-lived electronic states, allowing the sequential absorption of NIR photons at relatively low photon flux. The electrons climb the 4f Stark levels, absorbing multiple photons from the excitation source before relaxing back to the ground state upon emission of a photon with an energy higher than those from the source. While UCNPs are among the most efficient systems for converting NIR light to visible, they still hold key limitations, namely, they only weakly absorb incoming photons, hindering their external quantum efficiencies and overall performance. This thesis presents studies designed to enhance the efficiency and brightness of UCNPs. One method to circumvent the inherently weak absorption in UCNPs involves attaching organic dye antennae to the surface of the nanoparticles to absorb incoming light and funnel the absorbed energy into the UCNP. However, a detailed understanding of the energy transfer mechanism between dye and UCNP is required to fully realize the potential of this system. We propose, using a series of spectroscopic and kinetic measurements, that this energy transfer is mediated via the absorbing dye triplet state, and further that the intersystem crossing rate within the dye is enhanced by interactions with the heavy nuclei of the lanthanides within the UCNP. We then design a highly efficient dye:UCNP hybrid system utilizing this new understanding. Lastly we present a study highlighting the power and potential of using UCNPs for biological applications. Together these studies will advance the utilization of photon upconversion towards realizing its promise in applications.

Green-to-red photoconvertible fluorescent proteins (PCFPs) are key players in advanced microscopy schemes such as photoactivated localization microscopy (PALM). Whereas photoconversion and red-state blinking in PCFPs have been studied intensively, their green-state photophysical behavior has received less attention. Yet dark states in green PCFPs can become strongly populated in PALM schemes and exert an indirect but considerable influence on the quality of data recorded in the red channel. Furthermore, green-state photoswitching in PCFPs can be used directly for PALM and has been engineered to design highly efficient reversibly switchable fluorescent proteins (RSFPs) amenable to various nanoscopy schemes. Here, we demonstrate that green mEos4b efficiently switches to a long-lived dark state through cis-trans isomerization of its chromophore, as do most RSFPs. However, by combining kinetic crystallography, molecular dynamics simulations, and Raman spectroscopy, we find that the dark state in green mEos4b is much more dynamic than that seen in switched-off green IrisFP, a biphotochromic PCFP engineered from the common EosFP parent. Our data suggest that H-bonding patterns maintained by the chromophore in green PCFPs and RSFPs in both their on- and off-states collectively control photoswitching quantum yields. The reduced number of H-bonds maintained by the dynamic dark chromophore in green mEos4b thus largely accounts for the observed lower switching contrast as compared to that of IrisFP. We also compare the long-lived dark states reached from green and red mEos4b, on the basis of their X-ray structures and Raman signatures. Altogether, these data provide a unifying picture of the complex photophysics of PCFPs and RSFPs. ispartof: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol:142 issue:25 pages:10978-10988 ispartof: location:United States status: published

Directed transport of singlet excitation energy is a key process in natural light-harvesting systems and a desired feature in assemblies of functional organic molecules for organic electronics and nanotechnology applications. However, progress in this direction is hampered by the lack of concepts and model systems. Here we demonstrate an all-optical approach to manipulate singlet exciton transport pathways within supramolecular nanostructures via singlet-triplet annihilation, i.e., to enforce an effective motion of singlet excitons along a predefined direction. For this proof-of-concept, we locally photo-generate a long-lived triplet exciton population and subsequently a singlet exciton population on single bundles of H-type supramolecular nanofibres using two temporally and spatially separated laser pulses. The local triplet exciton population operates as a gate for the singlet exciton transport since singlet-triplet annihilation hinders singlet exciton motion across the triplet population. We visualize this manipulation of singlet exciton transport via the fluorescence signal from the singlet excitons, using a detection-beam scanning approach combined with time-correlated single-photon counting. Our reversible, all-optical manipulation of singlet exciton transport can pave the way to realising new design principles for functional photonic nanodevices.

Nuclear spin hyperpolarization provides a promising route to overcome the challenges imposed by the limited sensitivity of nuclear magnetic resonance. Here we demonstrate that dissolution of spin-polarized pentacene-doped naphthalene crystals enables transfer of polarization to target molecules via intermolecular cross relaxation at room temperature and moderate magnetic fields (1.45$\,$T). This makes it possible to exploit the high spin polarization of optically polarized crystals while mitigating the challenges of its transfer to external nuclei, particularly of the large distances and prohibitively weak coupling between source and target nuclei across solid-solid or solid-liquid interfaces. With this method, here we inject the highly polarized mixture into a benchtop NMR spectrometer and observe the polarization dynamics for target $^1$H nuclei. Although the spectra are radiation damped due to the high naphthalene magnetization, we describe a procedure to process the data in order to obtain more conventional NMR spectra, and extract the target nuclei polarization. With the entire process occurring on a timescale of one minute, we observe NMR signals enhanced by factors between -200 and -1730 at 1.45$\,$T for a range of small molecules., 8 pages, 4 figures

WOS:000381778400004; International audience; Recent experiments replacing oxygen atoms by sulfur in thymine have revealed that absorption and intersystem crossing properties of these derivatives are strongly dependent on the position and number of the substitutions, affecting their potential performance for photodynamical therapy. Using multireference quantum chemical methods (CASPT2 and DFT/MRCI), we calculated absorption spectra and spin orbit coupling matrix elements for thymine (Thy), 2-thiothymine (2tThy), 4-thiothymine (4tThy), and 2,4-dithiothymine (2,4dtThy), to investigate this relation between structure and photophysics. The simulations showed that a simple 4-electrons/4-orbital minimum model can explain the main experimentally observed spectral features. Moreover, the computational estimate of intersystem crossing lifetimes in this sequence of molecules revealed that the experimental value attributed to thymine in water might be underestimated by a factor 20, most probably due to an overlap of singlet/triplet absorption signals in the transient absorption spectrum. The difference between the absorptivity of 2tThy and 2tThd was also investigated, but no conclusive explanation could be found.

Here we report the application of readily prepared and available coumarin dyes for photoredox catalysis, which are able to mimic powerful reductant [Ir(iii)] complexes. Coumarin derivatives 9 and 10 were employed as photoreductants in pinacol coupling and in other reactions, in the presence of Et3N as a sacrificial reducing agent. As the electronic, photophysical, and steric properties of coumarins could be varied, a wide applicability to several classes of photoredox reactions is predicted.

Six new thiophene oligomers, here designated as tripodal-like oligothienyl imidazoles, were synthesized and have been investigated in ethanol solution at room and low temperature. The oligomers bear a common core where two or more thiophenes are linked to one or more imidazole unit which further links through its alpha position to a different number of incremental thiophene units. The study involves a comprehensive spectral and photophysical investigation where the properties of the singlet and triplet states have been investigated regarding absorption, fluorescence and phosphorescence, transient triplet-triplet absorption together with all relevant quantum yields (fluorescence, internal conversion, intersystem crossing and singlet oxygen) and lifetimes. In addition, DFT quantum chemical calculations were performed to gain a detailed understanding of the molecular geometry and optical properties of the investigated oligomers. From the overall data, the radiative (kF) and radiationless (kNR, kIC and kISC) rate constants have been determined and it is shown that, in contrast with the parent oligothiophenes, the radiative competes with the radiationless deactivation channels. The results show that, by comparison with the oligothiophene counterparts, there is an augment of the relative contributions of the internal conversion and fluorescence processes relative to the S1~~T1 intersystem crossing. Phosphosphorescence emission was found for the simplest member of the investigated compounds, with a low quantum yield and a lifetime of 8 picos. The data also show that the introduction of a 4,5-dithienyl-imidazole moiety in a bi- or terthiophene oligomer results in, respectively, a 20-fold and a 3-fold increase of the fluorescence quantum yield relative to their oligothiophene counterparts., Fundação para a Ciência e a Tecnologia (FCT)

Nuclear orientation via electron spin locking (NOVEL) is a technique to orient nuclear spins embedded in a solid. Like other methods of dynamic nuclear polarization (DNP) it employs a small amount of unpaired electron spins and uses a microwave field to transfer the polarization of these unpaired electron spins to the nuclear spins. Traditional DNP uses CW microwave fields, but NOVEL uses pulsed electron spin resonance (ESR) techniques: a 90 degree pulse-90 degree phase shift-locking pulse sequence is applied and during the locking pulse the polarization transfer is assured by satisfying the Hartmann-Hahn condition. The transfer is coherent and similar to coherence transfer between nuclear spins. However, NOVEL requires an extension of the existing theory to many, inequivalent nuclear spins and to arbitrary, i.e. high electron and nuclear spin polarization. In this paper both extensions are presented. The theory is applied to the system naphthalene doped with pentacene, where the proton spins are polarized using the photo-excited triplet states of the pentacene molecules and found to show excellent agreement with the experimentally observed evolution of the polarization transfer during the locking pulse.

Low-spin ground states and low-lying excited states of higher spin were investigated for four pyrene oxoverdazyl monoradicals 14 and eight pyrene dioxoverdazyl diradicals 512. The ground states for quartet and quintet spin symmetries that are in reality excited states were found in the region of 565-775 nm above the respective electronic ground states. We calculated the adiabatic magnetic exchange coupling constant in the electronic ground state of each isolated biradical (5-12) by unrestricted density functional theory. A number of hybrid functionals such as B3LYP, PBE0, M06, and M06-2X were used. We also used range-separated functionals such as LC-omega PBE and omega B97XD to compare their effects on the coupling constant and the relative energy of the high-spin state. Molecular geometries were optimized for the doublet and quartet spin states of every monoradical (14), and the broken symmetry and triplet solutions were optimized for every biradical (512), by systematically using 6-311G, 6-311G(d,p), and 6-311++G(d,p) basis sets with each functional. The geometry of each quintet diradical (512) was optimized using 6-311G basis set. B3LYP produced the best spin values. The excited state (quartet or quintet)ground state energy difference (Delta E) increases in the presence of para-phenylene connectors. These energy differences were predicted here. The nature of spin coupling and consequently the ground state spin agree with spin alternation rule and the calculated atomic spin population. The adiabatic coupling constants were predicted for the biradicals (5-12) in their electronic ground states. Electron paramagnetic resonance parameters were determined at 6-311++G** level for the ground state and the quartet state of 1 and compared with the available experimental data. Low-lying excited states were found for the radical center (oxoverdazyl), pyrene, molecule 1, and diradical 5 by time-dependent density functional theory (TDDFT) method using B3LYP hybrid, 6-311++G(d,p) basis set, and the molecular geometry in the electronic ground state. Data from these calculations were used to discuss possible mechanisms for the achievement of the high-spin (excited) states in 1 and 5 and to predict a similar outcome for radicals 24 and 612 upon excitation. A comprehensive mechanism for the first excitation is proposed here. In particular, we show that the initial excitation of 1 involves large contributions from mixed transitions between pyrene and oxoverdazyl moieties, whereas the initial excitation of 5 is basically that of only the pyrene fragment. Subsequent internal conversion and intersystem crossing are likely to lead to the high-spin states of lower energy. Sample spin-flip TDDFT calculations were also done to confirm the energetic location and composition of the quartet state of 1 and the quintet state of 5.

Photoinduced charge separation and recombination in a carotenoid-porphyrin-fullerene triad C-P-C 6 0 (Bahr et al., 2000) have been followed by time-resolved electron paramagnetic resonance. The electron-transfer process has been characterized in a glass of 2-methyltetrahydrofuran and in the nematic phase of two uniaxial liquid crystals (E-7 and ZLI-1167). In all the different media, the molecular triad undergoes two-step photoinduced electron transfer, with the generation of a long-lived charge-separated state (C . + -P-C 6 0 . - ), and charge recombination to the triplet state, localized in the carotene moiety, mimicking different aspects of the photosynthetic electron-transfer process. The magnetic interaction parameters have been evaluated by simulation of the spin-polarized radical pair spectrum. The weak exchange interaction parameter (J = +1.7 ′ 0.1 G) provides a direct measure of the dominant electronic coupling matrix element V between the C . + -P-C 6 0 . - radical pair state and the recombination triplet state 3 C-P-C 6 0 . Comparison of the estimated values of V for this triad and a structurally related triad differing only in the porphyrin bridge (octaalkylporphyrin vs tetraarylporphyrin) explains in terms of an electronic coupling effect the ∼6-fold variation of the recombination rate induced by the modification of the porphyrin bridge as derived by kinetic experiments (Bahr et al., 2000).

A matrix EPR spectroscopy study of the low temperature γ radiolysis of precipitated (Zeosil) and mesoporous high surface silica has afforded evidence of the formation of trapped H-atoms, H-atom centers, siloxy radicals ≡Si-O(•), anomalous silyl peroxy radicals ≡Si-OO(•) with reduced g tensor anisotropy, siloxy radical-cations (≡Si-O-Si≡)(+•), E' centers, and two species from Ge impurity. Coordination of peroxyl radicals with diamagnetic ≡Si(+) centers is proposed and tested by DFT computations in order to justify the observed g tensor. Coordination of H-atoms to ≡Si(+) centers is also proposed for the structure of the H-atom centers as an alternative model not requiring the intervention of Ge, Sn, or CO impurities. The DFT method has been employed to assess the electronic structure of siloxy radical-cations and its similarity with that of the carbon radical-cation analogues; the results have prompted a revision of the structures proposed in the literature for ST1 and ST2 centers. The comparison between the two types of silica has afforded evidence of different radiolysis mechanisms leading to a greater yield of trapped H-atoms and H-atom centers in zeosil silica, which is reckoned with the 4-fold greater concentration of silanol groups. Parallel radiolysis experiments carried out by using both types of silica with polybutadiene oligomers as adsorbate have afforded evidence of free valence and energy migration phenomena leading to irreversible linking of polybutadiene chains onto silica. Reaction mechanisms are proposed based on the detection of SiO2-bonded free radicals whose structure has been defined by EPR.

Funding: Marie Curie Early Stage Training network QIPEST (Grant No. MESTCT-2005-020505), the EPSRC through QIP IRC (Grant Nos. GR/S82176/01 and GR/S15808/01), the National Research Foundation and Ministry of Education, Singapore, the DAAD (German Academic Exchange Service), Linacre College, Oxford, and the Royal Society. Molecular nanostructures are promising building blocks for future quantum technologies, provided methods of harnessing their multiple degrees of freedom can be identified and implemented. Due to low decoherence rates, nuclear spins are considered ideal candidates for storing quantum information, while optical excitations can give rise to fast and controllable interactions for information processing. A recent paper [M. Schaffry et al., Phys. Rev. Lett. 104, 200501 (2010)] proposed a method for entangling two nuclear spins through their mutual coupling to a transient optically excited electron spin. Building on the same idea, we present here an extended and much more detailed theoretical framework, showing that this method is in fact applicable to a much wider class of molecular structures than previously discussed in the original proposal. Publisher PDF

A new optical-fiber-based spectrofluorometer for in vivo or in vitro detection of delayed fluorescence is presented and characterized. This compact setup is designed so that it can be readily adapted for future clinical use. Optical excitation is done with a nitrogen laser-pumped, tunable dye laser, emitting in the UV-vis part of the spectrum. Excitation and luminescence signals are carried to and from the biological tissues under investigation, located out of the setup enclosure, by a single optical fiber. These measurements, as well as measurements performed without a fiber on in vitro samples in a thermostable quartz cell, in a controlled-atmosphere enclosure, are possible due to the efficient collection of the laser-induced luminescence light which is collected and focused on the detector with a high aperture parabolic mirror. The detection is based on a gated photomultiplier which allows for time-resolved measurements of the delayed fluorescence intensity. Thus, relevant luminescence lifetimes, typically in the sub-microsecond-to-millisecond range, can be measured with near total rejection of the sample's prompt fluorescence. The instrument spectral and temporal resolution, as well as its sensitivity, is characterized and measurement examples are presented. The primary application foreseen for this setup is the monitoring and adjustment of the light dose delivered during photodynamic therapy. (C) 2011 Society of Photo-Optical Instrumentation Engineers (SPIE). [DOI: 10.1117/1.3558846]

The emission properties of some aza-stilbenes (2-, 3- and 4-styrylpyridine) and thio-stilbenes [2- and 3-styrylthiophene and 1,2-di-(3-thienyl)ethene] have been investigated after inclusion in commercial (NaY) and cation-exchanged (TlY) faujasite zeolites to get information on the triplet properties through population of the T 1 state induced by the heavy atom effect. The fluorescence properties in NaY and TlY were compared with those reported in solution. The phosphorescence spectra, observed in TlY at liquid nitrogen temperature, allowed the energy levels of the T 1 states to be obtained. Phosphorescence lifetimes were also measured. Their comparison with the lifetime known for stilbene showed that the radiative decay is little affected by the heteroatoms.

Immobilization of [60]fullerene onto gamma-Al(2)O(3) surface provides new heterogeneous photocatalysts for the oxidation of organic Compounds under oxygen atmosphere. These catalysts have been prepared by simple or Successive incipient wetness impregnation (using an organic solvent) followed by air-heating at 180 degrees C. In the C(60)/Al(2)O(3) system. C(60) loading was varied in the range of 1-4% (w/w). Several experimental techniques including BET. XRD, DRS, TGA, microelectrophoresis, photoluminescence and kinetic extraction, have been used to characterize these catalytic materials. It was found that the quite high surface exposed by the supported C(60) increases with the amount of the supported C(60), while the dispersion of the supported C(60) decreases. The quite stable supported [60]fullerene phase is comprised from C(60) clusters, small and large aggregates. This non-uniform size distribution is reflected to a non-uniform distribution concerning the 'supported phase-support' interactions. These interactions decrease with the amount of the supported C(60). The photocatalysts prepared may be safely used Lip to 200 degrees C. Above this temperature the supported C(60) is sublimated/combusted in air. The photocatalytic activity of the so-obtained catalytic systems has been evaluated in terms of substrate conversion in the singlet oxygen 'ene' reaction of alkenes. The photooxygenation of 2-methyl-2-heptene has been examined as a probe reaction. It was round that the catalytic activity increases with the increasing amount of the supported C(60) up to the value of 3% (w/w) and then decreases. The intrinsic activity expressed as TON or TOF decreased monotonically with C(60). In all cases, however. the photocatalytic activity of the Al(2)O(3)-supported C(60) catalysts was substantially increased compared to the unsupported C(60) precursor, exhibiting quantitative conversion yields after short reaction times. The catalytic behavior was attributed to the aforementioned opposite trends which follow the surface exposed by the supported C(60) on one hand and the 'supported C(60)-support' interactions and the C(60) dispersion on the other hand. The easy separation of these solid catalysts from the reaction mixture, the high activity and stability as well as the retained activity in subsequent catalytic cycles. make these supported catalysts suitable for a small-scale synthesis. (C) 2009 Elsevier B.V. All rights reserved. Journal of Molecular Catalysis a-Chemical

The steady state and time resolved fluorescence and the triplet-triplet absorption of p-dimethylaminobenzonitrile (DMABN) in presence of alpha- and beta-cyclodestrin (CD) were investigated at various host and guest concentrations and temperatures. The formation of 1:1 and 1:2 DMABN:alpha-CD and 1:1 and 2:2 complexes DMABN:beta-CD complexes was ascertained by applying global analysis methods. The "pure" fluorescence spectra as well as the emission quantum yields and lifetimes and the triplet properties of the various associates were determined. The role of environmental features in the radiative and non-radiative deactivation of the LE and ICT excited states of the complexed DMABN was elucidated.

The structure of the excited state of low-spin ferric heme o has been studied using picosecond time-resolved resonance Raman spectroscopy. The excited state has a lifetime of 10–30 ps, and the heme skeletal vibrations are shifted to lower frequencies relative to those in the electronic ground state. Based on the relatively small frequency shifts, we conclude that the relatively long-lived heme o excited state is not a porphyrin ππ * state. We propose that the heme o excited state is a charge transfer state, in which the heme iron donates an electron to the porphyrin macrocycle.

Low sensitivity is the primary limitation to extendingnuclearmagnetic resonance (NMR) techniques to more advanced chemical andstructural studies. Photochemically induced dynamic nuclear polarization(photo-CIDNP) is an NMR hyperpolarization technique where light isused to excite a suitable donor-acceptor system, creating aspin-correlated radical pair whose evolution drives nuclear hyperpolarization.Systems that exhibit photo-CIDNP in solids are not common, and thiseffect has, up to now, only been observed for C-13 and N-15 nuclei. However, the low gyromagnetic ratio and naturalabundance of these nuclei trap the local hyperpolarization in thevicinity of the chromophore and limit the utility for bulk hyperpolarization.Here, we report the first example of optically enhanced solid-state H-1 NMR spectroscopy in the high-field regime. This is achievedvia photo-CIDNP of a donor-chromophore-acceptor moleculein a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusionamong the abundant strongly coupled H-1 nuclei relays polarizationthrough the whole sample, yielding a 16-fold bulk H-1 signalenhancement under continuous laser irradiation at 450 nm. These findingsenable a new strategy for hyperpolarized NMR beyond the current limitsof conventional microwave-driven DNP.