Macrocyclic Ligand Coordinating Amide-Arm Hydrolysis Reaction Activation in Aqueous Solutions: Tetravalent Uranium Does It Better.

Chelation of lanthanide and actinide cations within a suitable macrocyclic ligand often results in a rigid, kinetically inert, and thermodynamically stable complex. A benchmark for such cation-ligand suitability are cyclen-derived macrocyclic ligands, frequently used as large cation hosts for various applications. Herein, a comprehensive study of the 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane ligand (DOTAM) chelates of UIV and CeIII and their properties in aqueous solutions is presented. By employing multiple analysis techniques, including X-ray crystallography, UV-vis absorbance, 1H NMR, UPLC-MS, cyclic voltammetry, and differential pulse voltammetry, the study has revealed that the two aqueous complexes undergo a spontaneous, gradual, and stepwise hydrolysis of each of the coordinated amides toward carboxylates. The coordination of UIV in the studied reaction has been shown to significantly enhance the reaction rate, leading to an acceleration of up to 6 orders of magnitude compared to the natural process of simple aqueous amides at room temperature. An attempt to describe the unusual chelated metal cation amide-activation feature, based on the relatively lower rigidity of the complex structure, is presented. Additionally, the electrochemical properties of the complex series are discussed in detail, along with the limitations of the analytical methods employed.

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen-Based Complexes and Clusters in Aqueous Solutions.

The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [CeIV 6 (O)4 (OH)4 (H2 O)8 (DOTAH)4 ] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [CeIV DOTP] and [CeIII DOTP(H2 O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [CeIV DOTA(H2 O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.

A bilayer coating as an oxygen-transfer cascade for the electrochemical ambient conversion of methane to oxygenates.

Oxidation of methane at ambient conditions to useful oxygenates at a bilayer-coated electrode is demonstrated. The composition of the coating, a Mn porphyrin mediator layer on top of a N(OH)2/NiOOH one, allows a cascade of oxygen transfer events upon applying a potential. It is shown, using (spectro)electrochemical techniques, density functional theory computations and product analytical methods, that formate and methanol accompanied by CO2 suppression can be observed at a certain potential range. This can lead to further development of similar oxygen/electron transfer cascades for possible use in devices for energy conversion and fuel/product generation.

Oligomers Intermediates in Between Two New Distinct Homonuclear Uranium(IV) DOTP Complexes*.

Two new aqueous UIV complexes were synthesized by the interaction between the tetravalent uranium cation and the (1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid) (DOTP) macrocyclic ligand. Two distinct homonuclear complexes were identified; the first was characterized by X-ray crystallography as a unique "out-of-cage", [U(DOTPH6 )2 ] complex, in which the UIV cation is octa-coordinated to 4 phosphonic arms from each ligand in a square anti-prism geometry, with a C4 symmetry. The second is the "in-cage" [U(DOTPH4 )] complex, in which the tetravalent cation is located between the macrocycle O4 and N4 planes. With the help of UV-Vis absorption, 1 H/31 P NMR, ATR-IR, and MALDI-TOFMS analytical techniques, the chemical interchange between both species is presented. It is shown that the one-way transition is governed by the formation of a multiple number of soluble oligomeric species consisting of varied stoichiometric ratios of both characterized homonuclear complexes.

DFT and Empirical Considerations on Electrocatalytic Water/Carbon Dioxide Reduction by CoTMPyP in Neutral Aqueous Solutions*.

A combined experimental and density functional theory (DFT) investigation was employed in order to examine the mechanism of electrochemical CO2 reduction and H2 formation from water reduction in neutral aqueous solutions. A water soluble cobalt porphyrin, cobalt [5,10,15,20-(tetra-N-methyl-4-pyridyl)porphyrin], (CoTMPyP), was used as catalyst. The possible attachment of different axial ligands as well as their effect on the electrocatalytic cycles were examined. A cobalt porphyrin hydride is a key intermediate which is generated after the initial reduction of the catalyst. The hydride is involved in the formation of H2 and formate and acts as an indirect proton source for the formation of CO in these H+ -starving conditions. The experimental results are in agreement with the computations and give new insights into electrocatalytic mechanisms involving water soluble metalloporphyrins. We conclude that in addition to the porphyrin's structure and metal ion center, the electrolyte surroundings play a key role in dictating the products of CO2 /H2 O reduction.

On the Aqueous Chemistry of the UIV -DOTA Complex.

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of UIV with H2 O, OH- , and F- as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The UIV -DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The UIV /UIII redox couple was found to be quasi-reversible for the complex with both axially bonded H2 O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron UV /UIV oxidation of the [UIV (DOTA)(H2 O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated UV cation.

Enhancement of photoelectrochemical organics degradation and power generation by electrodeposited coatings of g-C3N4 and graphene on TiO2 nanotube arrays.

New g-C3N4 coatings obtained via electropolymerization (EP) of melamine followed by a heat treatment and graphene oxide (GO) coatings based on combining GO sheets via EP of GO phenolic groups are used to improve the performance of photoanodes composed of TiO2 nanotube arrays towards the photoelectrochemical (PEC) oxidation of methanol. This process, as examined in Na2CO3 solution (pH 11.4) for the two types of coatings and serving as a model for the degradation of an organic pollutant, demonstrates enhanced PEC performance as compared to that obtained using electrochemically reduced GO coatings. PEC oxidation currents obtained with 1 M methanol reach saturation at potentials as low as ∼-0.4 V vs. Ag/AgCl, with the highest saturation current density of ∼2.6 mA cm-2 and photon-to-current efficiency of 52% as observed for the new TiO2NTs/g-C3N4 photoanodes. Electrochemical impedance spectroscopy measurements for these photoanodes show a charge transfer resistance one order of magnitude lower than that obtained by the other types of coatings. This indicates an enhanced charge separation ability for the photogenerated electron-hole pairs and faster interfacial charge transfer between the electron donor (methanol) and acceptor (holes). It is also demonstrated that the process of organics degradation can be achieved not only via an applied potential but also in a galvanic photofuelcell with methanol and oxygen serving as the fuel and oxidant, respectively. The power densities achieved with the electrochemically prepared g-C3N4 photoanodes (∼0.5 mW cm-2) are at least one order of magnitude higher than those reported for other TiO2-based systems.

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am3+ and Pu3+) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H2O)]-, where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.