Two mononuclear ruthenium complexes [RuL(pic)3] ( 1 ) and [RuL(bpy)(pic)] ( 2 ) (H2L=2,6‐pyridinedicarboxylic acid, pic=4‐picoline, bpy=2,2′‐bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium‐based water oxidation catalysts using [Ce(NH4)2(NO3)6] (CeIV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnover s?1. Under acidic conditions, the equatorial 4‐picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the RuIII state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using CeIV as oxidant, [RuL(pic)2(H2O)]+ is proposed as the real water oxidation catalyst. 相似文献
We describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox‐potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH‐dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six‐coordinate [RuIV] center to yield an anionic seven‐coordinate [RuIV?OH]? intermediate is one of the key steps of a single‐site mechanism in which all species are anionic or neutral. These complexes are among the fastest single‐site catalysts reported to date. 相似文献
Two mononuclear ruthenium complexes [Ru(H2tcbp)(isoq)2] ( 1 ) and [Ru(H2tcbp)(pic)2] ( 2 ) (H4tcbp=4,4′,6,6′‐tetracarboxy‐2,2′‐bipyridine, isoq=isoquinoline, pic=4‐picoline) are synthesized and fully characterized. Two spare carboxyl groups on the 4,4′‐positions are introduced to enhance the solubility of 1 and 2 in water and to simultaneously allow them to tether to the electrode surface by an ester linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium‐tin‐oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding to a turnover frequency of 0.41 s?1. The low overpotential (0.17 V) of electrochemical water oxidation for 1 in the homogeneous solution enables water oxidation under visible light by using [Ru(bpy)3]2+ ( P1 ) (bpy=2,2′‐bipyridine) or [Ru(bpy)2(4,4′‐(COOEt)2‐bpy)]2+ ( P2 ) as a photosensitizer. In a three‐component system containing 1 or 2 as a light‐driven WOC, P1 or P2 as a photosensitizer, and Na2S2O8 or [CoCl(NH3)5]Cl2 as a sacrificial electron acceptor, a high turnover frequency of 0.81 s?1 and a turnover number of up to 600 for 1 under different catalytic conditions are achieved. In a photoelectrochemical system, the WOC 1 and photosensitizer are immobilized together on the photoanode. The electrons efficiently transfer from the WOC to the photogenerated oxidizing photosensitizer, and a high photocurrent density of 85 μA cm?2 is obtained by applying 0.3 V bias vs. NHE. 相似文献
Two dinuclear and one mononuclear ruthenium complexes containing neutral polypyridyl ligands have been synthesised as pre‐water oxidation catalysts and characterised by 1H and 13C NMR spectroscopy and ESI‐MS. Their catalytic water oxidation properties in the presence of [Ce(NH4)2(NO3)6] (CeIV) as oxidant at pH 1.0 have been investigated. At low concentrations of CeIV (5 mM ), high turnover numbers of up to 4500 have been achieved. An 18O‐labelling experiment established that both O atoms in the evolved O2 originate from water. Combined electrochemical study and electrospray ionisation mass spectrometric analysis suggest that ligand exchange between coordinated 4‐picoline and free water produces Ru aquo species as the real water oxidation catalysts. 相似文献
Four new charge‐neutral ruthenium(II) complexes containing dianionic Schiff base and isoquinoline or 4‐picoline ligands were synthesized and characterized by NMR and ESI‐MS spectroscopies, elemental analysis, and X‐ray diffraction. The complexes exhibited excellent chemical water oxidation activity and high stability under acidic conditions (pH 1.0) using (NH4)2Ce(NO3)6 as a sacrificial electron acceptor. The high catalytic activities of these complexes for water oxidation were sustained for more than 10 h at low concentrations. High turnover numbers of up to 3200 were achieved. A water nucleophilic attack mechanism was proposed. A RuV?O intermediate was detected during the catalytic cycle by high‐resolution mass spectrometry. 相似文献
Insight into how H2O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar‐to‐fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru‐based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high‐resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non‐innocent behavior, in which metal–ligand cooperation is an important part during the four‐electron oxidation of H2O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non‐innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2O. 相似文献
Two ruthenium acetylide complexes [Ru]?C≡C?C≡C?C(OR)(C3H5)2 ( 2 , R=H and 2 a , R=CH3; [Ru]=Cp(PPh3)2Ru) each with two cyclopropyl rings were synthesized from TMS?C≡C?C≡C?C(OH)(C3H5)2 ( 1 ; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF6 afforded the vinylidene complexes 3 and 3 a , respectively. When NH4PF6 was used, instead of KPF6, additional ring‐opening reaction took place on one of the three‐membered ring. Treatment of [Ru]Cl with 1,3‐butadiyne ( 6 ), bearing an epoxide ring, afforded acetylide complex 7 with a furyl ring. Treatment of 2 a with Ph3CPF6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C3H5)2}[PF6] ( 10 ), which was not isolated. Additions of various alcohols in a solution of 10 generated a number of disubstituted allenylidene complexes {[Ru]=C=C=C(OR)?C=C(C3H5)2}[PF6] ( 11 ). Treatment of 11 with K2CO3 afforded the acetylide complex 12 bearing a carbonyl group, characterized by single X‐ray diffraction analysis. Addition of a primary amine to 10 caused cleavage of the farthermost C=C bond and several allenylidene complexes {[Ru]=C=C=C(Me)(NHR)}[PF6] ( 18 ) were isolated. 相似文献
Two new luminescent ruthenium(II) polypyridyl complexes, [Ru(bpy)2(tpt‐phen)]Cl2 ( 1 ; bpy=2,2′‐bipyridine, tpt‐phen=triptycenyl‐1,10‐phenanthroline) and [Ru(phen)2(tpt‐phen)]Cl2 ( 2 ; phen=1,10‐phenanthroline), have been developed as potential nonviral vectors for DNA delivery. Photophysical and electrochemical properties of the complexes have been investigated and corroborated with electronic structure calculations. DNA condensation by these complexes has been investigated by UV/Vis and emission spectroscopy, circular dichroism spectroscopy, atomic force microscopy, dynamic light scattering, confocal microscopy, and electrophoretic mobility studies. These complexes interact with DNA and efficiently condense DNA into globular nanoparticles that are taken up efficiently by HeLa cells. DNA cleavage inability and biocompatibility of complexes have been explored. Both complexes have good gene transfection abilities. 相似文献
The catalytic reactivity of the high‐spin MnII pyridinophane complexes [(Py2NR2)Mn(H2O)2]2+ (R=H, Me, tBu) toward O2 formation is reported. With small macrocycle N‐substituents (R=H, Me), the complexes catalytically disproportionate H2O2 in aqueous solution; with a bulky substituent (R=tBu), this catalytic reaction is shut down, but the complex becomes active for aqueous electrocatalytic H2O oxidation. Control experiments are in support of a homogeneous molecular catalyst and preliminary mechanistic studies suggest that the catalyst is mononuclear. This ligand‐controlled switch in catalytic reactivity has implications for the design of new manganese‐based water oxidation catalysts. 相似文献
Water oxidation is a key reaction in natural photosynthesis and in many schemes for artificial photosynthesis. Inspired by energy challenges and the emerging understanding of photosystem II, the development of artificial molecular catalysts for water oxidation has become a highly active area of research in recent years. In this Focus Review, we describe recent achievements in the development of single‐site ruthenium catalysts for water oxidation with a particular focus on the overpotential of water oxidation. First, we introduce the general scheme to access the high‐valent ruthenium–oxo species, the key species of the water‐oxidation reaction. Next, the mechanisms of the O? O bond formation from the active ruthenium–oxo species are described. We then discuss strategies to decrease the onset potentials of the water‐oxidation reaction. We hope this Focus Review will contribute to the further development of efficient catalysts toward sustainable energy‐conversion systems. 相似文献
A dinuclear ruthenium complex [RuII(NCNHC O)(pic)2]22+ ( 2 ) was firstly prepared and characterized spectroscopically and electrochemically. Instead of the conventional ligand exchange, complex 2 dissociates in situ to afford two single‐site Ru aqua complexes, [RuII(OH2)(NCNHC O)(pic)2]+, which mediates water oxidation through proton‐coupled electron transfer events. In electrokinetic studies, complex 2 demonstrated a TOF of 150.3 s−1 comparable to those state‐of‐the‐art catalysts at neutral conditions. TONs of 2173 and 217 were attained in chemical and photochemical water oxidation when 2 was used as a catalyst, exhibiting good stability. Notably, a TOF of 1.3 s−1 was achieved at CAN‐driven water oxidation, which outperformed most of the reported single‐site Ru complexes, indicating that complex 2 is one of most active water oxidation catalysts (WOCs) to date. The unique coordination configuration and outstanding catalytic performance of complex 2 might shed light on the design of novel molecular WOCs. 相似文献
Two new charge‐neutral iridium complexes, [Ir(tfm‐ppy)2(N,N′‐diisopropyl‐benzamidinate)] ( 1 ) and [Ir(tfm‐ppy)2(N,N′‐diisopropyl‐4‐diethylamino‐3,5‐dimethyl‐benzamidinate)] ( 2 ) (tfm‐ppy=4‐trifluoromethyl‐2‐phenylpyridine) containing an amidinate ligand and two phenylpyridine ligands were designed and characterised. The photophysical properties, electrochemical behaviours and emission quenching properties of these species were investigated. In concert with the cobalt catalyst [Co(bpy)3]2+, members of this new class of iridium complexes enable the photocatalytic generation of hydrogen from mixed aqueous solutions via an oxidative quenching pathway and display long‐term photostability under constant illumination over 72 h; one of these species achieved a relatively high turnover number of 1880 during this time period. In the case of complex 1 , the three‐component homogeneous photocatalytic system proved to be more efficient than a related system containing a charged complex, [Ir(tfm‐ppy)2(dtb‐bpy)]+ ( 3 , dtb‐bpy=4,4′‐di‐tert‐butyl‐2,2′‐dipyridyl). In combination with a rhodium complex as a water reduction catalyst, the performances of the systems using both complexes were also evaluated, and these systems exhibited a more efficient catalytic propensity for water splitting than did the cobalt‐based systems that have been studied previously. 相似文献
Oxygen formation through water oxidation catalysis is a key reaction in the context of fuel generation from renewable energies. The number of homogeneous catalysts that catalyze water oxidation at high rate with low overpotential is limited. Ruthenium complexes can be particularly active, especially if they facilitate a dinuclear pathway for oxygen bond formation step. A supramolecular encapsulation strategy is reported that involves preorganization of dilute solutions (10?5 m ) of ruthenium complexes to yield high local catalyst concentrations (up to 0.54 m ). The preorganization strategy enhances the water oxidation rate by two‐orders of magnitude to 125 s?1, as it facilitates the diffusion‐controlled rate‐limiting dinuclear coupling step. Moreover, it modulates reaction rates, enabling comprehensive elucidation of electrocatalytic reaction mechanisms. 相似文献
Arene control : Anticancer complexes [Ru(arene)Cl(en)]+ (arene=p‐cymene or biphenyl; en=ethylenediamine) bind to surface histidine (His128, His247, His510) and methionine (Met298) residues in human albumin, but only the p‐cymene complex can gain entry to the crevice containing the free cysteine thiolate (Cys34) and induce oxidation to sulfinate.