Synthesis of Ce(IV) Heteroleptic Double-Decker Complex with a New Helical Naphthalocyanine as a Potential Gearing Subunit.

This paper describes the synthesis of a cerium(IV)-based molecular gear composed of a thioether functionalized phthalocyanine anchoring ligand, and a helical naphthalocyanine rotating cogwheel functionalized with four carbazoles. The naphthalocyanine ligand 9 was obtained after eleven steps (overall yield of 0.2 %) as a mixture of three geometrical isomers, two of which are chiral and exhibit high levels of steric hindrance, as shown by DFT calculations.

Synthesis and Dynamic Behavior of Ce(IV) Double-Decker Complexes of Sterically Hindered Phthalocyanines.

Phthalocyanines and their double-decker complexes are interesting in designing rotative molecular machines, which are crucial for the development of molecular motors and gears. This study explores the design and synthesis of three bulky phthalocyanine ligands functionalized at the α-positions with phenothiazine or carbazole fragments, aiming to investigate dynamic rotational motions in these sterically hindered molecular complexes. Homoleptic and heteroleptic double-decker complexes were synthesized through the complexation of these ligands with Ce(IV).

Lipid cubic phase with an organic-inorganic hybrid structure formed by organoalkoxysilane lipid.

A lipid cubic phase encompassing a cross-linked siloxane structure was formed by the self-assembly of a synthetic organoalkoxysilane lipid in water. The spontaneous sol-gel reaction of the alkoxysilane moiety on the lipid head group produced an organic-inorganic hybrid material with a double gyroid 3 cubic structure.

Multiply engaged molecular gears composed of a cerium(IV) double-decker of a triptycene-functionalized porphyrin.

Intramolecular gearing motions are studied in a cerium(IV) double-decker of triptycene-functionalised porphyrins using single crystal X-ray analysis and variable temperature H-NMR.

Self-activated Rh-Zr mixed oxide as a nonhazardous cocatalyst for photocatalytic hydrogen evolution.

Efficient, robust and environmentally friendly cocatalysts for photocatalysts are important for large-scale solar hydrogen production. Herein, we demonstrate that a Rh-Zr mixed oxide is an efficient cocatalyst for hydrogen evolution. Impregnation of Zr and Rh precursors (Zr/Rh = 5 wt/wt%) formed RhZrO cocatalyst particles on Al-doped SrTiO, which exhibited 31× higher photocatalytic water-splitting activity than a RhO cocatalyst.

Synthesis of Bis{-Tetrakis(4--alkylpyridiniumyl)porphyrinato}cerium and Its Redox Switching Behavior.

A novel double-decker porphyrin complex, bis{-tetrakis(4--alkylpyridiniumyl)porphyrinato}cerium, was prepared. Electrochemical measurements revealed that this complex exhibited reversible redox waves corresponding to a 1e redox reaction of the cerium center. Treating the complex alternately with an oxidant and a reductant resulted in the reversible redox switching between the oxidized and reduced states in an organic solvent.

Dipolar Nanocars Based on a Porphyrin Backbone.

Invited for the cover of this issue is Gwénaël Rapenne and co-workers from CEMES-CNRS at University Paul Sabatier, Toulouse, France and from NAIST, Nara, Japan. The image depicts an artistic representation of a nanocar race. Read the full text of the article at 10.

Dipolar Nanocars Based on a Porphyrin Backbone.

The design and synthesis of a new family of nanocars is reported. To control their motion, we integrated a dipole which can be tuned thanks to strategic donor and acceptor substituents at the 5- and 15-positions of the porphyrin backbone. The two other meso positions are substituted with ethynyltriptycene moieties which are known to act as wheels.

Phase-segregated NiP @FeP O core@shell nanoparticles: ready-to-use nanocatalysts for electro- and photo-catalytic water oxidation through activation by structural transformation and spontaneous ligand removal.

The high overpotential of the oxygen evolution reaction is a critical issue to be overcome to realize efficient overall water splitting and enable hydrogen generation powered by sunlight. Homogeneous and stable nanoparticles (NPs) dispersed in solvents are useful as both electrocatalysts and cocatalysts of photocatalysts for the electro- and photo-catalytic oxygen evolution reaction, respectively, through their adsorption on various electrode substrates. Here, phase-segregated NiP @FeP O core@shell NPs are selectively synthesized by the reaction of Fe(CO) with amorphous NiP seed-NPs.

Kinetically "locked" metallomacrocycle.

Self-assembly based on reversible metal-ligand bond formation is useful for the synthesis of discrete supramolecular nanoarchitectures. However, the architectures constructed by this technique sometimes suffer from kinetic instability due to the dissociation of metal-ligand bonds, especially under highly diluted conditions or in the presence of competitive ligands or metal ions. In this study, a kinetically stabilized metallomacrocycle was synthesized in one pot via the combination of metal-mediated self-assembly and subsequent oxidative "locking" of the coordination bonds.