Platinum chromophore-based systems for photoinduced charge separation: a molecular design approach for artificial photosynthesis

Photoinduced charge separation is a fundamental step in photochemical energy conversion. In the design of molecularly based systems for light-to-chemical energy conversion, this step is studied through the construction of two- and three-component systems (dyads and triads) having suitable electron donor and acceptor moieties placed at specific positions on a charge-transfer chromophore. The most extensively studied chromophores in this regard are ruthenium(II) tris(diimine) systems with a common 3MLCT excited state, as well as related ruthenium(II) bis(terpyridyl) systems. This Forum contribution focuses on dyads and triads of an alternative chromophore, namely, platinum(II) di- and triimine systems having acetylide ligands. These d8 chromophores all possess a 3MLCT excited state in which the lowest unoccupied molecular orbital is a pi orbital on the heterocyclic aromatic ligand. The excited-state energies of these Pt(II) chromophores are generally higher than those found for the ruthenium(II) tris(diimine) systems, and the directionality of the charge transfer is more certain. The first platinum diimine bis(arylacetylide) triad, constructed by attaching phenothiazene donors to the arylacetylide ligands and a nitrophenyl acceptor to 5-ethynylphenanthroline of the chromophore, exhibited a charge-separated state of 75-ns duration. The first Pt(tpy)(arylacetylide)+-based triad contains a trimethoxybenzamide donor and a pyridinium acceptor and has been structurally characterized. The triad has an edge-to-edge separation between donor and acceptor fragments of 27.95 Angstroms. However, while quenching of the emission is complete for this system, transient absorption (TA) studies reveal that charge transfer does not move onto the pyridinium acceptor. A new set of triads described in detail here and having the formula [Pt(NO2phtpy)(p-C triple-bond C-C6H4CH2(PTZ-R)](PF6), where NO2phtpy = 4'-{4-[2-(4-nitrophenyl)vinyl]phenyl}-2,2';6',2'-terpyridine and PTZ = phenothiazine with R = H, OMe, possess an unsaturated linkage between the chromophore and a nitrophenyl acceptor. While the parent chromophore [Pt(ttpy)(C triple-bond CC6H5)]PF6 is brightly luminescent in a fluid solution at 298 K, the triads exhibit complete quenching of the emission, as do the related donor-chromophore (D-C) dyads. Electrochemically, the triads and D-C dyads exhibit a quasi-reversible oxidation wave corresponding to the PTZ ligand, while the R = H triad and related C-A dyad display a facile quasi-reversible reduction assignable to the acceptor. TA spectroscopy shows that one of the triads possesses a long-lived charge-separated state of approximately 230 ns.     

Observation of a re-entrant isotropic phase in a pure disc-like liquid crystal

Abstract

We report the observation of an optically isotropic phase in the new disc-like mesogen 2,3,7,8,12,13-hexa(octadecanoyloxy)truxene. On cooling, this optically isotropic phase goes over into a nematic phase, while on heating a columnar phase grows in. To our knowledge this is the first example of a pure discotic mesogen exhibiting an isotropic phase below the temperature existence of a columnar phase. Our findings are supported by refractive index measurements of this compound as a function of temperature.     

Insight into Oxide‐Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts

Reaction of (TBBP)AlMe ? THF with [Cp*₂Zr(Me)OH] gave [(TBBP)Al(THF)?O?Zr(Me)Cp*₂] (TBBP=3,3’,5,5’‐tetra‐tBu‐2,2'‐biphenolato). Reaction of [DIPPnacnacAl(Me)?O?Zr(Me)Cp₂] with [PhMe₂NH]⁺[B(C₆F₅)₄]^? gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)?O?Zr(THF)Cp₂]⁺[B(C₆F₅)₄]^? (DIPPnacnac=HC[(Me)C=N(2,6‐iPr₂?C₆H₃)]₂). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40–47 kcal mol^?1) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six‐membered‐ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal‐Me‐C angle that prevents synchronized bond‐breaking and making. A more‐likely pathway is dissociation of the Al‐O‐Zr complex into an aluminate and the active polymerization catalyst [Cp*₂ZrMe]⁺.     

Pflanzenchemie

Analytical and Bioanalytical Chemistry -     

Brownian fluctuations and heating of an optically aligned gold nanorod

We present the first quantitative measurements of the torque exerted on a single gold nanorod in a polarized three-dimensional optical trap. We determined the torque both by observing the time-averaged orientation distribution and by measuring the dynamics of the rotational brownian fluctuations. The measurements are in good agreement with calculations, where the temperature profile around the hot nanorod gives rise to a reduced, effective viscosity. The maximum torque on a 60 nm×25 nm nanorod was 100 pN·nm, large enough to address single-molecule processes in soft and biological matter.     

The picosecond transient Raman spectra of S1 excited oligophenyls, oxazols and stilbene derivatives

Picosecond time-resolved resonance Raman spectra of electronically excited laser-dye molecules, oligophenyls, oxazols, and stilbene derivatives in solution have been obtained. The spectral profiles of several transients are observed to change on the picosecond timescale.     

Molecular weight control of polyacrylamide with sodium formate as a chain‐transfer agent: Characterization via size exclusion chromatography/multi‐angle laser light scattering and determination of chain‐transfer constant

We discuss the synthesis and characterization of polyacrylamide (PAM) homopolymers with carefully controlled molecular weights (MWs). PAM was synthesized via free‐radical solution polymerization under conditions that yield highly linear polymer with minimal levels of hydrolysis. The MW of the PAM homopolymers was controlled by the addition of sodium formate (NaOOCH) to the polymerization medium as a conventional chain‐transfer agent. MWs and polydispersity indices (PDIs) were determined via size exclusion chromatography/multi‐angle laser light scattering analysis; for polymerizations carried out to high conversion, PAM MWs ranged from 0.23 to 6.19 × 10⁶ g/mol, with most samples having PDI ≈2.0. Zero‐shear intrinsic viscosities of the polymers were determined via low‐shear viscometry in 0.514 M NaCl at 25 °C. Data derived from the polymer characterization were used to determine the chain‐transfer constant to NaOOCH under the given polymerization conditions and to calculate Mark–Houwink–Sakurada K and a values for PAM in 0.514 M NaCl at 25 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 560–568, 2003     

An investigation of the changes in the natural frequency of a pile affected by scour

Scour around bridge foundations is one of the leading causes of bridge failure. Up until recently, the monitoring of this phenomenon was primarily based around using underwater instrumentation to monitor the progression of scour holes as they develop around foundation systems. Vibration-based damage detection techniques have been used to detect damage in bridge beams. The application of these vibration based methods to the detection of scour has come to the fore in research in recent years. This paper examines the effect that scour has on the frequency response of a driven pile foundation system, similar to those used to support road and rail bridges. The effect of scour on the vibration characteristics of the pile is examined using laboratory and field testing. It is clear that there is a very clear reduction in the natural frequency of the pile as the severity of scour increases. It is shown that by combining state-of-the-art geotechnical techniques with relatively simple finite element modelling approaches, it is possible to accurately predict the natural frequency of the pile for a given scour depth. Therefore, the paper proposes a method that would allow the estimation of scour depth for a given observed pile frequency.     

Modeling of material properties after ultrashort laser and XUV excitation

By means of first principles calculations, we studied the possibility of manipulating structural properties of different materials via excitation with intense femtosecond laser or extreme ultraviolet (XUV) pulses. For silicon and boron-nitride nanotubes, we performed ab initio molecular dynamics simulations using the code CHIVES, developed in our group, to describe their laser-induced structural dynamics. For both materials, we determined the damage thresholds. We also investigated the structural response of magnesium and copper to ultrashort XUV excitation. For this purpose, we performed frozen-phonon calculations based on all-electron density functional theory and allowed the possibility of core-hole excitation. We found that Cu undergoes bond hardening and Mg bond softening upon creation of core holes and hot electrons, where we defined the bond strength by the vibrational frequencies.