Through-bond interactions and the localization of excited-state dynamics

The influence of through-bond interactions on nonadiabatic excited-state dynamics is investigated by time-resolved photoelectron spectroscopy (TRPES) and ab initio computation. We compare the dynamics of cyclohexa-1,4-diene, which exhibits a through-bond interaction known as homoconjugation (the electronic correlation between nonconjugated double bonds), with the nonconjugated cyclohexene. Each molecule was initially excited to a 3s Rydberg state using a 200 nm femtosecond pump pulse. The TRPES spectra of these molecules display similar structure and time constants on a subpicosecond time scale. Our ab initio calculations show that similar sets of conical intersections (a [1,2]- and [1,3]-hydrogen shift, as well as carbon-carbon bond cleavage) are energetically accessible to both molecules and that the geometry and orbital composition at the minimum energy crossing points to the ground state are directly analogous. These experimental and computational results suggest that the excited-state dynamics of cyclohexa-1,4-diene become localized at a single double bond and that the effects of through-bond interaction, dominant in the absorption spectrum, are absent in the excited-state dynamics. The notion of excited-state dynamics being localized at specific sites within the nuclear framework is analogous to the localization of light absorption by a subsystem within the molecule, designated a chromophore. We propose the utility of the analogous concept, denoted here as a dynamophore.     

Microsecond charge recombination in a linear triarylamine-Ru(bpy)3(2+)-anthraquinone triad

Linear triads with ruthenium photosensitizers are frequently based on the Ru(terpyridine)(2)(2+) unit. We report on vectorial photoinduced electron transfer in a linear triad based on the Ru(bipyridine)(3)(2+) photosensitizer. Electron-hole separation over a 22 ?-distance is established with a quantum yield greater than 64% and persists for 1.3 μs in acetonitrile.     

Theoretical reconstruction and elementwise analysis of photoelectron spectra for imidazolium-based ionic liquids

We have recently measured core level and valence band XPS, UPS, and MIES spectra of two room temperature ionic liquids composed of bis(trifluoromethylsulfonyl)imide anions ([Tf(2)N](-)) and either 1-ethyl-3-methyl-imidazolium ([EMIm](+)) or 1-octyl-3-methyl-imidazolium cations ([OMIm](+)). [T. Ikari, A. Keppler, M. Reinm?ller, W. J. D. Beenken, S. Krischok, M. Marschewski, W. Maus-Friedrichs, O. H?fft and F. Endres, e-J. Surf. Sci. Nanotechnol., 2010, 8, 241.] In the present work we analyze these spectra by means of partial density of states (pDOS) as calculated from a single ion pair of the respective ionic liquid using density functional theory (DFT). Subsequently we reconstruct the XPS and UPS spectra by considering photoemission cross sections and analyze the MIES spectra by pDOS, which provides us decisive hints to the ionic liquid surface structure.     

Building custom polysaccharides in vitro with an efficient, broad-specificity xyloglucan glycosynthase and a fucosyltransferase

The current drive for applications of biomass-derived compounds, for energy and advanced materials, has led to a resurgence of interest in the manipulation of plant polymers. The xyloglucans, a family of structurally complex plant polysaccharides, have attracted significant interest due to their intrinsic high affinity for cellulose, both in muro and in technical applications. Moreover, current cell wall models are limited by the lack of detailed structure-property relationships of xyloglucans, due to a lack of molecules with well-defined branching patterns. Here, we have developed a new, broad-specificity "xyloglucan glycosynthase", selected from active-site mutants of a bacterial endoxyloglucanase, which catalyzed the synthesis of high molar mass polysaccharides, with complex side-chain structures, from suitable glycosyl fluoride donor substrates. The product range was further extended by combination with an Arabidopsis thaliana α(1→2)-fucosyltransferase to achieve the in vitro synthesis of fucosylated xyloglucans typical of dicot primary cell walls. These enzymes thus comprise a toolkit for the controlled enzymatic synthesis of xyloglucans that are otherwise impossible to obtain from native sources. Moreover, this study demonstrates the validity of a chemo-enzymatic approach to polysaccharide synthesis, in which the simplicity and economy of glycosynthase technology is harnessed together with the exquisite specificity of glycosyltransferases to control molecular complexity.     

Vibrational energy redistribution in catechol during ultraviolet photolysis

This article reports the striking interplay between the molecular structure and the photodissociation dynamics of catechol (a key dihydroxybenzene), identified using a combination of electronic spectroscopy, hydrogen (Rydberg) atom photofragment translational spectroscopy, density functional theory and second order approximate coupled cluster methods. We describe how the non-planar (C(1) symmetry) ← planar (C(s) symmetry) geometry change during S(1) (1(1)ππ*) ←S(0) excitation in catechol, as well as the presence of internal hydrogen bonding, can perturb the photodissociation dynamics relative to that of phenol (a monohydroxybenzene), particularly with respect to O-H bond fission via the lowest dissociative (1)πσ* state. For λ(phot) > 270 nm, O-H bond fission (of the non hydrogen bonded hydroxyl moiety) is deduced to proceed via H atom tunnelling from the photo-prepared 1(1)ππ* state into the lowest (1)πσ* state of the molecule. The vibrational energy distribution in the resulting catechoxyl product changes notably as λ(phot) is tuned on resonance with either the v' = 0, m(2)' = 1(+) or m(2)' = 2(+) torsional levels of the photo-prepared 1(1)ππ* state: the product state distribution is highly sensitive to the degree of OH torsional excitation (m(2)) prepared during photo-excitation. It is deduced that such torsional excitation can be redistributed very efficiently into ring puckering (and likely also in-plane ring stretch) vibrations as the molecule tunnels to its repulsive 1(1)πσ* state and dissociates. These observations can be rationalised by consideration of the photo-prepared nuclear wavefunctions. Analysis of the product vibrational energy distribution also reveals that the O-H bond strength of the non hydrogen bonded O-H moiety in catechol, D(0)(H-catechoxyl) ≤ 27?480 ± 50 cm(-1), ～2500 cm(-1) lower than that of the sole O-H bond in bare phenol. As a consequence, the vertical excitation energy of the 1(1)πσ* state in catechol is reduced relative to that in phenol, yielding a particularly broad distribution of product vibrations for λ(phot) < 270 nm. This study highlights the interplay between molecular geometry and redistribution of vibrational energy during ultraviolet photolysis of phenols.     

Surface investigation of intermetallic PdGa(111)

The intermetallic PdGa is a highly selective and potent catalyst in the semihydrogenation of acetylene, which is attributed to the surface stability and isolated Pd atom ensembles. In this context PdGa single crystals of form B with (111) orientation were investigated by means of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), X-ray photoelectron diffraction (XPD), and low-energy electron diffraction (LEED) to study the electronic and geometric properties of this surface. UPS and thermal desorption spectroscopy (TDS) were used to probe the chemisorption behavior of CO. The PdGa(111) surface exhibits a (1 × 1) LEED and a pronounced XPD pattern indicating an unreconstructed bulk-truncated surface. Low-temperature STM reveals a smooth surface with a (1 × 1) unit cell. No segregation occurs, and no impurities are detected by XPS. The electronic structure and the CO adsorption properties reveal PdGa(111) to be a bulk-truncated intermetallic compound with Pd-Ga partial covalent bonding.     

Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins

Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure–reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an Ir^II–H bond dissociation free energy around 44 kcal mol⁻¹, which is formed after reductive ³MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer.

Upon irradiation with visible light, an iridium hydride complex undergoes hydrogen atom transfer (HAT) to unactivated olefins in presence of a sacrificial electron donor and a proton source.