Oleg G. Poluektov

Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (•)OH radicals (oxidation product) from water, and CO(3)(-) radical anions (oxidation product) from carbonates, was detected in CO(2)-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (•)OCH(3), and methyl, (•)CH(3), radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO(2) on the surface of TiO(2) is supported by the results of first-principles calculations.

Sodium insertion in carboxylate based materials and their application in 3.6 V full sodium cells

The sodium battery has the potential to be the next generation rechargeable system which utilizes cheaper and more abundant sodium material but affords nearly the same power as lithium batteries. One of the key barriers for the sodium battery is the lack of stable anode materials which can insert sodium ions reversibly at relatively low potential. This contribution reports the sodium insertion in a series of organic carboxylate based materials: (C8H4Na2O4), (C8H6O4), (C8H5NaO4), (C8Na2F4O4), (C10H2Na4O8), (C14H4O6) and (C14H4Na4O8) at low voltage (below 0.6 V vs. Na/Na+). These organic anode materials can insert reversibly up to 2 Na per molecule with good cycleability. The Na insertion mechanism was proposed and 3.6 V full sodium batteries were made and cycled reversibly at room temperature and at 55 °C.

A Bioinspired Construct That Mimics the Proton Coupled Electron Transfer between P680*† and the Tyrz-His190 Pair of Photosystem II

A bioinspired hybrid system, composed of colloidal TiO2 nanoparticles surface modified with a photochemically active mimic of the PSII chlorophyll-Tyr-His complex, undergoes photoinduced stepwise electron transfer coupled to proton motion at the phenolic site. Low temperature electron paramagnetic resonance studies reveal that injected electrons are localized on TiO2 nanoparticles following photoexcitation. At 80 K, 95% of the resulting holes are localized on the phenol moiety and 5% are localized on the porphyrin. At 4.2 K, 52% of the holes remain trapped on the porphyrin. The anisotropic coupling tensors of the phenoxyl radical are resolved in the photoinduced D-band EPR spectra and are in good agreement with previously reported g-tensors of tyrosine radicals in photosystem II. The observed temperature dependence of the charge shift is attributed to restricted nuclear motion at low temperature and is reminiscent of the observation of a trapped high-energy state in the natural system. Electrochemical studies show that the phenoxyl/phenol couple of the model system is chemically reversible and thermodynamically capable of water oxidation.

Millisecond coherence time in a tunable molecular electronic spin qubit

Quantum information processing (QIP) could revolutionize areas ranging from chemical modeling to cryptography. One key figure of merit for the smallest unit for QIP, the qubit, is the coherence time (T2), which establishes the lifetime for the qubit. Transition metal complexes offer tremendous potential as tunable qubits, yet their development is hampered by the absence of synthetic design principles to achieve a long T2. We harnessed molecular design to create a series of qubits, (Ph4P)2[V(C8S8)3] (1), (Ph4P)2[V(β-C3S5)3] (2), (Ph4P)2[V(α-C3S5)3] (3), and (Ph4P)2[V(C3S4O)3] (4), with T2s of 1–4 μs at 80 K in protiated and deuterated environments. Crucially, through chemical tuning of nuclear spin content in the vanadium(IV) environment we realized a T2 of ∼1 ms for the species (d20-Ph4P)2[V(C8S8)3] (1′) in CS2, a value that surpasses the coordination complex record by an order of magnitude. This value even eclipses some prominent solid-state qubits. Electrochemical and continuous wave electron paramagnetic resonance (EPR) data reveal variation in the electronic influence of the ligands on the metal ion across 1–4. However, pulsed measurements indicate that the most important influence on decoherence is nuclear spins in the protiated and deuterated solvents utilized herein. Our results illuminate a path forward in synthetic design principles, which should unite CS2 solubility with nuclear spin free ligand fields to develop a new generation of molecular qubits.

A bioinspired redox relay that mimics radical interactions of the Tyr–His pairs of photosystem II

In water-oxidizing photosynthetic organisms, light absorption generates a powerfully oxidizing chlorophyll complex (P680(•+)) in the photosystem II reaction centre. This is reduced via an electron transfer pathway from the manganese-containing water-oxidizing catalyst, which includes an electron transfer relay comprising a tyrosine (Tyr)-histidine (His) pair that features a hydrogen bond between a phenol group and an imidazole group. By rapidly reducing P680(•+), the relay is thought to mitigate recombination reactions, thereby ensuring a high quantum yield of water oxidation. Here, we show that an artificial reaction centre that features a benzimidazole-phenol model of the Tyr-His pair mimics both the short-internal hydrogen bond in photosystem II and, using electron paramagnetic resonance spectroscopy, the thermal relaxation that accompanies proton-coupled electron transfer. Although this artificial system is much less complex than the natural one, theory suggests that it captures the essential features that are important in the function of the relay.

Spin signatures of photogenerated radical anions in polymer-[70]fullerene bulk heterojunctions: high frequency pulsed EPR spectroscopy.

Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C(60)-PCBM), and two different soluble C(70)-derivates: C(70)-PCBM and diphenylmethano[70]fullerene oligoether (C(70)-DPM-OE). The first experimental identification of the negative polaron localized on the C(70)-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P(+) and P(-) in PHT-C(70) bulk heterojunctions. Comparing signals from C(70)-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C(70) molecule.

High-field pulsed EPR and ENDOR of Gd3+ complexes in glassy solutions

In this work D-band pulsed electron paramagnetic resonance was used to record the field-sweep spectra of several Gd3+ complexes in glassy water-methanol solutions. These spectra were analyzed by a specially developed stochastic superposition model that predicted the essential features of the distribution of the crystal field interaction (CFI) parameters in glassy systems. As a result of this analysis, the CFI distributions for the studied complexes were evaluated. The D-band Mims1H electron-nuclear double resonance spectra were free from CFI-related distortions, which allowed us to accurately determine the hyperfine interaction (HFI) parameters for water ligand protons and to unequivocally establish that the HFI distribution is solely related to the distribution of the Gd−H distances.

Protein Delivery of a Ni Catalyst to Photosystem I for Light-Driven Hydrogen Production

The direct conversion of sunlight into fuel is a promising means for the production of storable renewable energy. Herein, we use Natures specialized photosynthetic machinery found in the Photosystem I (PSI) protein to drive solar fuel production from a nickel diphosphine molecular catalyst. Upon exposure to visible light, a self-assembled PSI-[Ni(P2(Ph)N2(Ph))2](BF4)2 hybrid generates H2 at a rate 2 orders of magnitude greater than rates reported for photosensitizer/[Ni(P2(Ph)N2(Ph))2](BF4)2 systems. The protein environment enables photocatalysis at pH 6.3 in completely aqueous conditions. In addition, we have developed a strategy for incorporating the Ni molecular catalyst with the native acceptor protein of PSI, flavodoxin. Photocatalysis experiments with this modified flavodoxin demonstrate a new mechanism for biohybrid creation that involves protein-directed delivery of a molecular catalyst to the reducing side of Photosystem I for light-driven catalysis. This work further establishes strategies for constructing functional, inexpensive, earth-abundant solar fuel-producing PSI hybrids that use light to rapidly produce hydrogen directly from water.

Cobaloxime-Based Artificial Hydrogenases

Cobaloximes are popular H2 evolution molecular catalysts but have so far mainly been studied in nonaqueous conditions. We show here that they are also valuable for the design of artificial hydrogenases for application in neutral aqueous solutions and report on the preparation of two well-defined biohybrid species via the binding of two cobaloxime moieties, {Co(dmgH)2} and {Co(dmgBF2)2} (dmgH2 = dimethylglyoxime), to apo Sperm-whale myoglobin (SwMb). All spectroscopic data confirm that the cobaloxime moieties are inserted within the binding pocket of the SwMb protein and are coordinated to a histidine residue in the axial position of the cobalt complex, resulting in thermodynamically stable complexes. Quantum chemical/molecular mechanical docking calculations indicated a coordination preference for His93 over the other histidine residue (His64) present in the vicinity. Interestingly, the redox activity of the cobalt centers is retained in both biohybrids, which provides them with the catalytic activity for H2 evolution in near-neutral aqueous conditions.

Multiple quantum coherences from hyperfine transitions in a vanadium(IV) complex.

We report a vanadium complex in a nuclear-spin free ligand field that displays two key properties for an ideal candidate qubit system: long coherence times that persist at high temperature, T2 = 1.2 μs at 80 K, and the observation of quantum coherences from multiple transitions. The electron paramagnetic resonance (EPR) spectrum of the complex [V(C8S8)3](2-) displays multiple transitions arising from a manifold of states produced by the hyperfine coupling of the S = ½ electron spin and I = 7/2 nuclear spin. Transient nutation experiments reveal Rabi oscillations for multiple transitions. These observations suggest that each pair of hyperfine levels hosted within [V(C8S8)3](2-) are candidate qubits. The realization of multiple quantum coherences within a transition metal complex illustrates an emerging method of developing scalability and addressability in electron spin qubits. This study presents a rare molecular demonstration of multiple Rabi oscillations originating from separate transitions. These results extend observations of multiple quantum coherences from prior reports in solid-state compounds to the new realm of highly modifiable coordination compounds.