Tuning the Photo-electrochemical Performance of RuII-Sensitized Two-Dimensional MoS2

Covalently tethering photosensitizers to catalytically active 1T-MoS₂ surfaces holds great promise for the solar-driven hydrogen evolution reaction (HER). Herein, we report the preparation of two new Ru^II-complex-functionalized MoS₂ hybrids [Ru^II(bpy)₂(phen)]-MoS₂ and [Ru^II(bpy)₂(py)Cl]-MoS₂. The influence of covalent functionalization of chemically exfoliated 1T-MoS₂ with coordinating ligands and Ru^II complexes on the HER activity and photo-electrochemical performance of this dye-sensitized system was studied systematically. We find that the photo-electrochemical performance of this Ru^II-complex-sensitized MoS₂ system is highly dependent on the surface extent of photosensitizers and the catalytic activity of functionalized MoS₂. The latter was strongly affected by the number and the kind of functional groups. Our results underline the tunability of the photovoltage generation in this dye-sensitized MoS₂ system by manipulation of the surface functionalities, which provides a practical guidance for smart design of future dye-sensitized MoS₂ hydrogen production devices towards improved the photofuel conversion efficiency.     

Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles

β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.     

What’s New with the Neutron and Proton

The existence and importance of the proton radius puzzle, observed via a Lamb shift measurement in muonic atoms, is discussed. Possible resolutions of the puzzle are discussed. Then the broader question of the meaning of the proton radius is addressed and examples of correctly defined charge densities are presented.     

A universality theorem for ratios of random characteristic polynomials

We consider asymptotics of ratios of random characteristic polynomials associated with orthogonal polynomial ensembles. Under some natural conditions on the measure in the definition of the orthogonal polynomial ensemble we establish a universality limit for these ratios.     

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Supramolecular polymers are a class of macromolecules stabilized by weak non‐covalent interactions. These self‐assembled aggregates typically undergo stimuli‐induced reversible assembly and disassembly. They thus hold great promise as so‐called functional materials. In this work, we present the design, synthesis, and responsive behavior of a short supramolecular oligomeric system based on two hetero‐complementary subunits. These “monomers” consist of a tetrathiafulvalene‐functionalized calix[4]pyrrole (TTF‐C[4]P) and a glycol diester‐linked bis‐2,5,7‐trinitrodicyanomethylenefluorene‐4‐carboxylate (TNDCF), respectively. We show that when mixed in organic solvents, such as CHCl₃, CH₂ClCH₂Cl, and methylcyclohexane, supramolecular aggregation takes place to produce short oligomers stabilized by hydrogen bonding and donor–acceptor charge‐transfer (CT) interactions. The self‐associated materials were characterized by ¹H NMR and UV/Vis/NIR absorption spectroscopy, as well as by concentration‐ and temperature‐dependent absorption spectroscopy and dynamic light scattering (DLS) analyses of both the monomeric and oligomerized species. The self‐associated system produced from TTF‐C[4]P and TNDCF exhibits a concentration‐dependent aggregation behavior typical of supramolecular polymers. Further support for the proposed self‐assembly came from theoretical calculations. The fluorescence emitting properties of TNDCF are quenched under conditions that promote the formation of supramolecular aggregates containing TTF‐C[4]P and TNDCF. This quenching effect has been utilized as a probe for the detection of substrates in the form of anions (i.e., chloride) and nitroaromatic explosives (i.e., 1,3,5‐trinitrobenzene). Specifically, the addition of these substrates to mixtures of TTF‐C[4]P and TNDCF produced a fluorescence “turn‐on” response.