Surface-Promoted Evolution of Ru-bda Coordination Oligomers Boosts the Efficiency of Water Oxidation Molecular Anodes.

A new Ru oligomer of formula {[RuII(bda-κ-N2O2)(4,4'-bpy)]10(4,4'-bpy)}, 10 (bda is [2,2'-bipyridine]-6,6'-dicarboxylate and 4,4'-bpy is 4,4'-bipyridine), was synthesized and thoroughly characterized with spectroscopic, X-ray, and electrochemical techniques. This oligomer exhibits strong affinity for graphitic materials through CH-π interactions and thus easily anchors on multiwalled carbon nanotubes (CNT), generating the molecular hybrid material 10@CNT. The latter acts as a water oxidation catalyst and converts to a new species, 10'(H2O)2@CNT, during the electrochemical oxygen evolution process involving solvation and ligand reorganization facilitated by the interactions of molecular Ru catalyst and the surface. This heterogeneous system has been shown to be a powerful and robust molecular hybrid anode for electrocatalytic water oxidation into molecular oxygen, achieving current densities in the range of 200 mA/cm2 at pH 7 under an applied potential of 1.45 V vs NHE. The remarkable long-term stability of this hybrid material during turnover is rationalized based on the supramolecular interaction of the catalyst with the graphitic surface.

Structure-Activity Relationship for Di- up to Tetranuclear Macrocyclic Ruthenium Catalysts in Homogeneous Water Oxidation.

Two di- and tetranuclear Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylate) macrocyclic complexes were synthesized and their catalytic activities in chemical and photochemical water oxidation investigated in a comparative manner to our previously reported trinuclear congener. Our studies have shown that the catalytic activities of this homologous series of multinuclear Ru(bda) macrocycles in homogeneous water oxidation are dependent on their size, exhibiting highest efficiencies for the largest tetranuclear catalyst. The turnover frequencies (TOFs) have increased from di- to tetranuclear macrocycles not only per catalyst molecule but more importantly also per Ru unit with TOF of 6 s-1 to 8.7 s-1 and 10.5 s-1 in chemical and 0.6 s-1 to 3.3 s-1 and 5.8 s-1 in photochemical water oxidation per Ru unit, respectively. Thus, for the first time, a clear structure-activity relationship could be established for this novel class of macrocyclic water oxidation catalysts.

Shape-Persistent Tetrahedral [4+6] Boronic Ester Cages with Different Degrees of Fluoride Substitution.

In recent years the interest of shape-persistent organic cage compounds synthesized by dynamic covalent chemistry (DCC) has risen, because these cages are potentially interesting for gas sorption or -separation. One such reaction in DCC is the condensation of boronic acids with diols to form boronic esters. Most interestingly, the variety of geometries and sizes for boronic ester cages is much lower than that of, for example, imine-based cages. Here, a small series of shape-persistent [4+6] tetrahedral boronic ester cages is introduced. One cage has a high specific surface area of 511 m2 g-1 and selectively adsorbs ethane over ethylene and acetylene.

Cucurbitimines - imine cages with concave walls.

The variety of shape-persistent organic cages by imine bond formation has tremendously enlarged in recent years by using different building blocks (aldehydes and amines) in the condensation reactions. Here, we describe the use of a kinked tetraldehyde to generate pumpkin-shaped cages with concave walls, similar to cucurbiturils.

Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation.

Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investigations revealed that the activities of these functionalized macrocycles in water oxidation are significantly affected by the position at which the substituents were introduced. Interestingly, this effect could not be explained based on the redox properties of the catalysts since these are not markedly influenced by the functionalization of the ligands. Instead, detailed investigations by X-ray crystal structure analysis and theoretical simulations showed that conformational changes imparted by the substituents are responsible for the variation of catalytic activities of the Ru macrocycles. For the first time, macrocyclic structure of this class of water oxidation catalysts is unequivocally confirmed and experimental indication for a hydrogen-bonded water network present in the cavity of the macrocycles is provided by crystal structure analysis. We ascribe the high catalytic efficiency of our Ru(bda) macrocycles to cooperative proton abstractions facilitated by such a network of preorganized water molecules in their cavity, which is reminiscent of catalytic activities of enzymes at active sites.