Robust Molecular Anodes for Electrocatalytic Water Oxidation Based on Electropolymerized Molecular Cu Complexes.

A multistep synthesis of a new tetra-amidate macrocyclic ligand functionalized with alkyl-thiophene moieties, 15,15-bis(6-(thiophen-3-yl)hexyl)-8,13-dihydro-5H-dibenzo[b,h][1,4,7,10]tetraazacyclotridecine-6,7,14,16(15H,17H)-tetraone, H4 L, is reported. The reaction of the deprotonated ligand, L4- , and Cu(II) generates the complex [LCu]2- , that can be further oxidized to Cu(III) with iodine to generate [LCu]- . The H4 L ligand and their Cu complexes have been thoroughly characterized by analytic and spectroscopic techniques (including X-ray Absorption Spectroscopy, XAS). Under oxidative conditions, the thiophene group of [LCu]2- complex polymerizes on the surface of graphitic electrodes (glassy carbon disks (GC), glassy carbon plates (GCp ), carbon nanotubes (CNT), or graphite felts (GF)) generating highly stable thin films. With CNTs deposited on a GC by drop casting, hybrid molecular materials labeled as GC/CNT@p-[LCu]2- are obtained. The latter are characterized by electrochemical techniques that show their capacity to electrocatalytically oxidize water to dioxygen at neutral pH. These new molecular anodes achieve current densities in the range of 0.4 mA cm-2 at 1.30 V versus NHE with an onset overpotential at ≈250 mV. Bulk electrolysis experiments show an excellent stability achieving TONs in the range of 7600 during 24 h with no apparent loss of catalytic activity and maintaining the molecular catalyst integrity, as evidenced by electrochemical techniques and XAS spectroscopy.

A photosensitizer-polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production.

Decoupling the production of solar hydrogen from the diurnal cycle is a key challenge in solar energy conversion, the success of which could lead to sustainable energy schemes capable of delivering H2 independent of the time of day. Here, we report a fully integrated photochemical molecular dyad composed of a ruthenium-complex photosensitizer covalently linked to a Dawson polyoxometalate that acts as an electron-storage site and hydrogen-evolving catalyst. Visible-light irradiation of the system in solution leads to charge separation and electron storage on the polyoxometalate, effectively resulting in a liquid fuel. In contrast to related, earlier dyads, this system enables the harvesting, storage and delayed release of solar energy. On-demand hydrogen release is possible by adding a proton donor to the dyad solution. The system is a minimal molecular model for artificial photosynthesis and enables the spatial and temporal separation of light absorption, fuel storage and hydrogen release.

Transforming Escherichia coli Proteomembranes into Artificial Chloroplasts Using Molecular Photocatalysis.

During the light-dependent reaction of photosynthesis, green plants couple photoinduced cascades of redox reactions with transmembrane proton translocations to generate reducing equivalents and chemical energy in the form of NADPH (nicotinamide adenine dinucleotide phosphate) and ATP (adenosine triphosphate), respectively. We mimic these basic processes by combining molecular ruthenium polypyridine-based photocatalysts and inverted vesicles derived from Escherichia coli. Upon irradiation with visible light, the interplay of photocatalytic nicotinamide reduction and enzymatic membrane-located respiration leads to the simultaneous formation of two biologically active cofactors, NADH (nicotinamide adenine dinucleotide) and ATP, respectively. This inorganic-biologic hybrid system thus emulates the cofactor delivering function of an active chloroplast.

Strong Ligand Stabilization Based on π-Extension in a Series of Ruthenium Terpyridine Water Oxidation Catalysts.

The substitution behavior of the monodentate Cl ligand of a series of ruthenium(II) terpyridine complexes (terpyridine (tpy)=2,2':6',2''-terpyridine) has been investigated. 1 H NMR kinetic experiments of the dissociation of the chloro ligand in D2 O for the complexes [Ru(tpy)(bpy)Cl]Cl (1, bpy=2,2'-bipyridine) and [Ru(tpy)(dppz)Cl]Cl (2, dppz=dipyrido[3,2-a:2',3'-c]phenazine) as well as the binuclear complex [Ru(bpy)2 (tpphz)Ru(tpy)Cl]Cl3 (3 b, tpphz=tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) were conducted, showing increased stability of the chloride ligand for compounds 2 and 3 due to the extended π-system. Compounds 1-5 (4=[Ru(tbbpy)2 (tpphz)Ru(tpy)Cl](PF6 )3 , 5=[Ru(bpy)2 (tpphz)Ru(tpy)(C3 H8 OS)/(H2 O)](PF6 )3 , tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine) are tested for their ability to run water oxidation catalysis (WOC) using cerium(IV) as sacrificial oxidant. The WOC experiments suggest that the stability of monodentate (chloride) ligand strongly correlates to catalytic performance, which follows the trend 1>2>5≥3>4. This is also substantiated by quantum chemical calculations, which indicate a stronger binding for the chloride ligand based on the extended π-systems in compounds 2 and 3. Additionally, a theoretical model of the mechanism of the oxygen evolution of compounds 1 and 2 is presented; this suggests no differences in the elementary steps of the catalytic cycle within the bpy to the dppz complex, thus suggesting that differences in the catalytic performance are indeed based on ligand stability. Due to the presence of a photosensitizer and a catalytic unit, binuclear complexes 3 and 4 were tested for photocatalytic water oxidation. The bridging ligand architecture, however, inhibits the effective electron-transfer cascade that would allow photocatalysis to run efficiently. The findings of this study can elucidate critical factors in catalyst design.

Localizing the initial excitation - A case study on NiO photocathodes using Ruthenium dipyridophenazine complexes as sensitizers.

We report on the localization of the initially excited electronic state within the molecular framework of a series of [Ru(bpy)2dppz]2+ derivatives (bpy:2,2'-bipyridine, dppz: dipyrido-phenazine) as sensitizers in NiO based photocathodes. The introduction of conjugated linkers with phenylene and triazole moieties in the bpy ligand sphere separates the NiO surface from the metal center and hence is considered to stabilize the charge separated state, which results from light-driven hole injection. However, introduction of the conjugated linkers also alters the localization of the excess electron density in the excited state within the ligand sphere and impacts the extent to which the charge-separated state is formed. The study emphasizes that tuning the ligand with the lowest-energy π* orbital distal or proximal to the NiO surface significantly affects the initial charge-separation and the solar cell performance. The stability of the charge-separated state correlates with the observed photocurrents in dye-sensitized solar cells. Furthermore, the study challenges the widely accepted concept that the introduction of extended anchoring groups, i.e. increasing Ru - NiO distance, stabilizes the charge-separated state and suppresses charge recombination at the metal-oxide molecule interface.

Tailored protective groups for surface immobilization of ruthenium dyes.

McKenna reaction conditions are applied to the [Ru(4,4'-(CH2PO3Et2)2(bpy)](PF6)2 model chromophore in order to obtain [Ru(4,4'-(CH2PO3TMS2)2(bpy)](Br2-x)(PF6)x (x = 0-2) (2) by replacing the alkyl moieties of the phosphonates with TMS groups (TMS = trimethylsilyl). The model complex is immobilized onto both NiO powder and NiO electrodes on FTO (fluorine doped tin oxide) using organic solvents. The stability of surface binding in aqueous media and the DSC performance of 2 are tested and compared to those of a conventional dye of structure [Ru(4,4'-(CH2PO3TBA2)2(bpy)](PF6)2 (1) (TBA = tetrabutyl ammonium). This is the first example of a ruthenium based chromophore with a phosphonic acid silyl-ester being directly immobilized onto a NiO surface. In addition, complex 2 exhibits superior stability towards desorption in aqueous media and at the same time showing improved DSC performance and stability in acetonitrile and a slightly higher dye loading on the electrode surface compared to 1.