Assessing Carbazole Derivatives as Single-Electron Photoreductants.

The electron-donating capabilities of carbazoles have stimulated interest in their use as photoinduced single-electron reductants. Due to the modularity of the carbazole, a further broadening and understanding of their reactivity could be achieved by manipulating the structure. Herein, eight carbazole derivatives were synthesized, characterized, and assessed as single-electron photoreductants in the hydrodehalogenation of aryl halides and the arylation of N-methylpyrrole.

Molecular Z-Scheme for Solar Fuel Production via Dual Photocatalytic Cycles.

Natural photosynthesis uses an array of molecular structures in a multiphoton Z-scheme for the conversion of light energy into chemical bonds (i.e., solar fuels). Here, we show that upon excitation of both a molecular photocatalyst (PC) and a substituted naphthol (ROH) in the presence of a sacrificial electron donor and proton source, we achieve photocatalytic synthesis of H2. Data support a multiphoton mechanism that is catalytic with respect to both PC and ROH. The use of a naphthol molecule as both a light absorber and H2 producing catalyst is a unique motif for Z-scheme systems. This molecular Z-scheme can drive a reaction that is uphill by 511 kJ mol-1 and circumvents the high-energy constraints associated with the reduction of weak acids in their ground state, thus offering a new paradigm for the production of solar fuels.

Role of Metal Ion-Linked Multilayer Thickness and Substrate Porosity in Surface Loading, Diffusion, and Solar Energy Conversion.

Metal ion-linked multilayers offer an easily prepared and modular architecture for controlling energy and electron transfer events on nanoparticle, metal oxide films. However, unlike with planar electrodes, the mesoporous nature of the films inherently limits both the thickness of the multilayer and subsequent diffusion through the pores. Here, we systematically investigated the role of TiO2 nanoparticle film porosity and metal ion-linked multilayer thickness in surface loading, through-pore diffusion, and overall device performance. The TiO2 porosity was controlled by varying TiO2 sintering times. Molecular multilayer thickness was controlled through assembling ZnII-linked bridging molecules (B = p-terphenyl diphosphonic acid) between the metal oxide and the Ru(bpy)2((4,4'-PO3H2)2bpy)]Cl2 dye (RuP), thus producing TiO2-(Bn)-RuP films. Using attenuated total reflectance infrared absorption and UV-vis spectroscopy, we observed that at least two molecular layers (i.e., TiO2-B2 or TiO2-B1-RuP) could be formed on all films but subsequent loading was dependent on the porosity of the TiO2. Rough estimates indicate that in a film with 34 nm average pore diameter, the maximum multilayer film thickness is on the order of 4.6-6 nm, which decreases with decreasing pore size. These films were then incorporated as the photoanodes in dye-sensitized solar cells with cobalt(II/III)tris(4,4'-di-tert-butyl-2,2'-bipyridine) as a redox mediator. In agreement with the surface-loading studies, electrochemical impedance spectroscopy measurements indicate that mediator diffusion is significantly hindered in films with thicker multilayers and less porous TiO2. Collectively, these results show that care must be taken to balance multilayer thickness, substrate porosity, and size of the mediator in designing and maximizing the performance of new multilayer energy and electron management architectures.

Phenalenannulations: Three-Point Double Annulation Reactions that Convert Benzenes into Pyrenes.

3-Point annulations, or phenalenannulations, transform a benzene ring directly into a substituted pyrene by "wrapping" two new cycles around the perimeter of the central ring at three consecutive carbon atoms. This efficient, modular, and general method for π-extension opens access to non-symmetric pyrenes and their expanded analogues. Potentially, this approach can convert any aromatic ring bearing a -CH2 Br or a -CHO group into a pyrene moiety. Depending upon the workup choices, the process can be directed towards either tin- or iodo-substituted product formation, giving complementary choices for further various cross-coupling reactions. The two-directional bis-double annulation adds two new polyaromatic extensions with a total of six new aromatic rings at a central core.