Solar Energy Storage: Competition between Delocalized Charge Transfer and Localized Excited States in the Norbornadiene to Quadricyclane Photoisomerization.

We describe for the first time the full reaction coordinate regarding the photoisomerization of red-absorbing norbornadienes (NBDs) to quadricyclanes (QCs). Our studies go beyond steady-state investigations by using an arsenal of time-resolved techniques. Importantly, the red absorption of NBDs is made possible by a different charge-transfer character; adjusting its strength enables control over the photoreversibility of the rearrangement. In the case of strong charge-transfer character (a weakly electron-withdrawing ester and a strongly electron-donating dimethylaniline), photoirradiation with visible light into the delocalized charge-transfer absorption of NBD affords QC reversibly. In stark contrast, UV photoirradiation into the NBD localized excited state leads to a photoinduced degradation and cannot be back-isomerized to NBD under any circumstances. If the charge-transfer character is weak (a weakly electron-withdrawing ester and a weakly electron-donating phenyl), reversibility is seen independently of the photoirradiation light.

Dynamic Kinetic Sensitization of ß-Dicarbonyl Compounds-Access to Medium-Sized Rings by De†Mayo-Type Ring Expansion.

Herein, we present a photocatalyzed two-carbon ring expansion of ß-dicarbonyl compounds with unactivated olefins that provides facile access to medium-sized rings. Selective sensitization of the substoichiometric enol tautomer enables reactivity of substrates incompatible with the classical De Mayo reaction conditions. Key to success is the identification of the metal-based sensitizer fac-[Ir(CF3 -pmb)3 ], which can be excited using common near-visible LEDs, and possesses a high triplet excited state energy of 73.3 kcal mol-1 . This exactly falls in the range between the triplet energies of the enol and keto tautomer, thereby enabling a dynamic kinetic sensitization. Demonstrating the applicability of fac-[Ir(CF3 -pmb)3 ] as a photocatalyst in organic synthesis for the first time, we describe a two-step photocycloaddition-ring-opening cascade with ß-ketoesters, -diketones, and -ketoamides. The mechanism has been corroborated by time-resolved spectroscopy, as well as further experimental and computational studies.

Controlling Solar Hydrogen Production by Organizing Porphyrins.

In this study, a highly efficient photocatalytic H2 production system is developed by employing porphyrins as photocatalysts. Palladium and platinum tetracarboxyporphyrins (PdTCP and PtTCP) are adsorbed or coadsorbed onto TiO2 nanoparticles (NPs), which act as the electron transport medium and as a scaffold that promotes the self-organization of the porphyrinoids. The self-organization of PdTCP and PtTCP, forming H- and J-aggregates, respectively, is the key element for H2 evolution, as in the absence of TiO2 NPs no catalytic activity is detected. Notably, J-aggregated PtTCPs are more efficient for H2 production than H-aggregated PdTCPs. In this approach, a single porphyrin, which self-organizes onto TiO2 NPs, acts as the light harvester and simultaneously as the catalyst, whereas TiO2 serves as the electron transport medium. Importantly, the concurrent adsorption of PdTCP and PtTCP onto TiO2 NPs results in the most efficient catalytic system, giving a turnover number of 22,733 and 30.2 mmol(H2 ) g(cat)-1 .

Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C-O vs. C-C double bonds.

Investigations into the selectivity of intermolecular alkyl radical additions to C-O- vs. C-C-double bonds in α,ß-unsaturated carbonyl compounds are described. Therefore, a photoredox-initiated radical chain reaction is explored, where the activation of the carbonyl-group through an in situ generated Lewis acid - originating from the substrate - enables the formation of either C-O or the C-C-addition products. α,ß-Unsaturated aldehydes form selectively 1,2-, while esters and ketones form the corresponding 1,4-addition products exclusively. Computational studies lead to reason that this chemo- and regioselectivity is determined by the consecutive step, i.e. an electron transfer, after reversible radical addition, which eventually propagates the radical chain.

Mixed Organic Ligand Shells: Controlling the Nanoparticle Surface Morphology toward Tuning the Optoelectronic Properties.

Precise control over the ratio of perylene bisimide (PBI) monomers and aggregates, immobilized on alumina nanoparticle (NP) surfaces, is demonstrated. Towards this goal, phosphonic acid functionalized PBI derivatives (PA-PBI) are shown to self-assemble into stoichiometrically mixed monolayers featuring aliphatic, glycolic, or fluorinated phosphonic acid ligands, serving as imbedding matrix (PA-M) to afford core-shell NPs. Different but, nevertheless, defined PBI monomer/aggregate composition is achieved by either the variation in the PA-PBI to PA-M ratios, or the utilization of different PA-Ms. Various steady-state as well as time-resolved spectroscopy techniques are applied to probe the core-shell NPs with respect to changes in their optical properties upon variations in the shell composition. To this end, the ratio between monomer and excimer-like emission assists in deriving information on the self-assembled monolayer composition, local ordering, and corresponding aggregate content. With the help of X-ray reflectivity measurements, accompanied by molecular dynamics simulations, the built-up of the particle shells, in general, and the PBI aggregation behavior, in particular, are explored in depth.

Resonant Tunneling Induced Enhancement of Electron Field Emission by Ultra-Thin Coatings.

The emission of electrons from the surface of a material into vacuum depends strongly on the material's work function, temperature, and the intensity of electric field. The combined effects of these give rise to a multitude of related phenomena, including Fowler-Nordheim tunneling and Schottky emission, which, in turn, enable several families of devices, ranging from vacuum tubes, to Schottky diodes, and thermionic energy converters. More recently, nanomembrane-based detectors have found applications in high-resolution mass spectrometry measurements in proteomics. Progress in all the aforementioned applications critically depends on discovering materials with effective low surface work functions. We show that a few atomic layer deposition (ALD) cycles of zinc oxide onto suspended diamond nanomembranes, strongly reduces the threshold voltage for the onset of electron field emission which is captured by resonant tunneling from the ZnO layer. Solving the Schroedinger equation, we obtain an electrical field- and thickness-dependent population of the lowest few subbands in the thin ZnO layer, which results in a minimum in the threshold voltage at a thickness of 1.08 nm being in agreement with the experimentally determined value. We conclude that resonant tunneling enables cost-effective ALD coatings that lower the effective work function and enhance field emission from the device.

The energy-transfer-enabled biocompatible disulfide-ene reaction.

Sulfur-containing molecules participate in many essential biological processes. Of utmost importance is the methylthioether moiety, present in the proteinogenic amino acid methionine and installed in tRNA by radical-S-adenosylmethionine methylthiotransferases. Although the thiol-ene reaction for carbon-sulfur bond formation has found widespread applications in materials or medicinal science, a biocompatible chemo- and regioselective hydrothiolation of unactivated alkenes and alkynes remains elusive. Here, we describe the design of a general chemoselective anti-Markovnikov hydroalkyl/aryl thiolation of alkenes and alkynes-also allowing the biologically important hydromethylthiolation-by triplet-triplet energy transfer activation of disulfides. This fast disulfide-ene reaction shows extraordinary functional group tolerance and biocompatibility. Transient absorption spectroscopy was used to study the sensitization process in detail. The hereby gained mechanistic insights were successfully employed for optimization of the catalytic system. This photosensitized transformation should stimulate bioimaging applications and carbon-sulfur bond-forming late-stage functionalization chemistry, especially in the context of metabolic labelling.

Multistep energy and electron transfer processes in novel rotaxane donor-acceptor hybrids generating microsecond-lived charge separated states.

A new set of [Cu(phen)2]+ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide-alkyne cycloaddition reaction (the "click" or CuAAC reaction) with Sauvage's metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C60 radical anion (C60˙-) and either one-electron oxidized porphyrin (ZnP˙+) or one-electron oxidized ferrocene (Fc˙+) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)2]2+ (τ < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc˙+; τ = 380-560 ns), or ZnP˙+ (τ = 2.3-8.4 µs), and C60˙- have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.

On-off switch of charge-separated states of pyridine-vinylene-linked porphyrin-C60 conjugates detected by EPR.

The design, synthesis, and electronic properties of a new series of D-π-A conjugates consisting of free base (H2P) and zinc porphyrins (ZnP) as electron donors and a fullerene (C60) as electron acceptor, in which the two electroactive entities are covalently linked through pyridine-vinylene spacers of different lengths, are described. Electronic interactions in the ground state were characterized by electrochemical and absorption measurements, which were further supported with theoretical calculations. Most importantly, charge-transfer bands were observed in the absorption spectra, indicating a strong push-pull behavior. In the excited states, electronic interactions were detected by selective photoexcitation under steady-state conditions, by time-resolved fluorescence investigations, and by pump probe experiments on the femto-, pico-, and nanosecond time scales. Porphyrin fluorescence is quenched for the different D-π-A conjugates, from which we conclude that the deactivation mechanisms of the excited singlet states are based on photoinduced energy- and/or electron transfer processes between H2P/ZnP and C60, mediated through the molecular spacers. The fluorescence intensity decreases and the fluorescence lifetimes shorten as the spacer length decreases and as the spacer substitution changes. With the help of transient absorption spectroscopy, the formation of charge-separated states involving oxidized H2P/ZnP and reduced C60 was confirmed. Lifetimes of the corresponding charge-separated states, which ranged from ∼400 picoseconds to 165 nanoseconds, depend on the spacer length, the spacer substitution, and the solvent polarity. Interestingly, D-π-A conjugates containing the longest linkers did not necessarily exhibit the longest charge-separated state lifetimes. The distances between the electron donors and the acceptors were calculated by molecular modelling. The longest charge-separated state lifetime corresponded to the D-π-A conjugate with the longest electron donor-acceptor distance. Likewise, EPR measurements in frozen media revealed charge separated states in all the D-π-A conjugates investigated. A sharp peak with g values ∼2.000 was assigned to reduced C60, while a broader, less intense signal (g ∼ 2.003) was assigned to oxidized H2P/ZnP. On-off switching of the formation and decay of the charge-separated states was detected by EPR at 77 K by repeatedly turning the irradiation source on and off.

A search for varying fundamental constants using hertz-level frequency measurements of cold CH molecules.

Many modern theories predict that the fundamental constants depend on time, position or the local density of matter. Here we develop a spectroscopic method for pulsed beams of cold molecules, and use it to measure the frequencies of microwave transitions in CH with accuracy down to 3 Hz. By comparing these frequencies with those measured from sources of CH in the Milky Way, we test the hypothesis that fundamental constants may differ between the high- and low-density environments of the Earth and the interstellar medium. For the fine structure constant we find Δα/α=(0.3 ± 1.1) × 10⁻7, the strongest limit to date on such a variation of α. For the electron-to-proton mass ratio we find Δµ/µ=(-0.7 ± 2.2) × 10⁻7. We suggest how dedicated astrophysical measurements can improve these constraints further and can also constrain temporal variation of the constants.

A stringent limit on a drifting proton-to-electron mass ratio from alcohol in the early universe.

The standard model of physics is built on the fundamental constants of nature, but it does not provide an explanation for their values, nor require their constancy over space and time. Here we set a limit on a possible cosmological variation of the proton-to-electron mass ratio µ by comparing transitions in methanol observed in the early universe with those measured in the laboratory. From radio-astronomical observations of PKS1830-211, we deduced a constraint of Δµ/µ = (0.0 ± 1.0) × 10(-7) at redshift z = 0.89, corresponding to a look-back time of 7 billion years. This is consistent with a null result.

A gravitationally lensed water maser in the early Universe.

Water masers are found in dense molecular clouds closely associated with supermassive black holes at the centres of active galaxies. On the basis of the understanding of the local water-maser luminosity function, it was expected that masers at intermediate and high redshifts would be extremely rare. However, galaxies at redshifts z > 2 might be quite different from those found locally, not least because of more frequent mergers and interaction events. Here we use gravitational lensing to search for masers at higher redshifts than would otherwise be possible, and find a water maser at redshift 2.64 in the dust- and gas-rich, gravitationally lensed type-1 quasar MG J0414+0534 (refs 6-13). The isotropic luminosity is 10,000 (, solar luminosity), which is twice that of the most powerful local water maser and half that of the most distant maser previously known. Using the locally determined luminosity function, the probability of finding a maser this luminous associated with any single active galaxy is 10(-6). The fact that we see such a maser in the first galaxy we observe must mean that the volume densities and luminosities of masers are higher at redshift 2.64.

Strong limit on a variable proton-to-electron mass ratio from molecules in the distant universe.

The Standard Model of particle physics assumes that the so-called fundamental constants are universal and unchanging. Absorption lines arising in molecular clouds along quasar sightlines offer a precise test for variations in the proton-to-electron mass ratio, mu, over cosmological time and distance scales. The inversion transitions of ammonia are particularly sensitive to mu as compared to molecular rotational transitions. Comparing the available ammonia spectra observed toward the quasar B0218+357 with new, high-quality rotational spectra, we present the first detailed measurement of mu with this technique, limiting relative deviations from the laboratory value to |Deltamu/mu| < 1.8 x 10(-6) (95% confidence level) at approximately half the universe's current age-the strongest astrophysical constraint to date. Higher-quality ammonia observations will reduce both the statistical and systematic uncertainties in these observations.

The geometric distance and proper motion of the Triangulum Galaxy (M33).

We measured the angular rotation and proper motion of the Triangulum Galaxy (M33) with the Very Long Baseline Array by observing two H2O masers on opposite sides of the galaxy. By comparing the angular rotation rate with the inclination and rotation speed, we obtained a distance of 730 +/- 168 kiloparsecs. This distance is consistent with the most recent Cepheid distance measurement. M33 is moving with a velocity of 190 +/- 59 kilometers per second relative to the Milky Way. These measurements promise a method to determine dynamical models for the Local Group and the mass and dark-matter halos of M31, M33, and the Milky Way.