A lithium-air battery and gas handling system demonstrator.

The lithium-air (Li-air) battery offers one of the highest practical specific energy densities of any battery system at >400 W h kgsystem-1. The practical cell is expected to operate in air, which is flowed into the positive porous electrode where it forms Li2O2 on discharge and is released as O2 on charge. The presence of CO2 and H2O in the gas stream leads to the formation of oxidatively robust side products, Li2CO3 and LiOH, respectively. Thus, a gas handling system is needed to control the flow and remove CO2 and H2O from the gas supply. Here we present the first example of an integrated Li-air battery with in-line gas handling, that allows control over the flow and composition of the gas supplied to a Li-air cell and simultaneous evaluation of the cell and scrubber performance. Our findings reveal that O2 flow can drastically impact the capacity of cells and confirm the need for redox mediators. However, we show that current air-electrode designs translated from fuel cell technology are not suitable for Li-air cells as they result in the need for higher gas flow rates than required theoretically. This puts the scrubber under a high load and increases the requirements for solvent saturation and recapture. Our results clarify the challenges that must be addressed to realise a practical Li-air system and will provide vital insight for future modelling and cell development.

Four Redox Isomers of a [3 × 3] Copper-Iron Heterometal Grid.

A mixed-valence heterometallic nonanuclear [3 × 3] grid complex, [CuI2CuII6FeIII(L)6](BF4)5·MeOH·9H2O (1; MeOH = methanol), was synthesized by a one-pot reaction of copper and iron ions with multidentate ligand 2,6-bis[5-(2-pyridinyl)-1H-pyrazol-3-yl]pyridine (H2L). 1 showed five quasi-reversible one-electron redox processes centered at +0.74, +0.60, +0.39, +0.27, and -0.13 V versus SCE, assignable to four CuI/CuII processes and one FeII/FeIII couple, respectively. The two-electron-oxidized species [CuII8FeIII(L)6](PF6)7·4MeOH·7H2O (12eOx), the two-electron-reduced species [CuI4CuII4FeIII(L)6](PF6)3·2H2O (12eRed), and the three-electron-reduced species [CuI4CuII4FeII(L)6](PF6)2·5MeOH·H2O (13eRed) were isolated electrochemically. The four redox isomers were characterized by single-crystal X-ray analysis, SQUID magnetometry, and Mössbauer spectroscopy.

Silver(I)-Catalyzed Synthesis of Cuneanes from Cubanes and their Investigation as Isosteres.

Bridged or caged polycyclic hydrocarbons have rigid structures that project substituents into precise regions of 3D space, making them attractive as linking groups in materials science and as building blocks for medicinal chemistry. The efficient synthesis of new or underexplored classes of such compounds is, therefore, an important objective. Herein, we describe the silver(I)-catalyzed rearrangement of 1,4-disubstituted cubanes to cuneanes, which are strained hydrocarbons that have not received much attention since they were first described in 1970. The synthesis of 2,6-disubstituted or 1,3-disubstituted cuneanes can be achieved with high regioselectivities, with the regioselectivity being dependent on the electronic character of the cubane substituents. A preliminary assessment of cuneanes as scaffolds for medicinal chemistry suggests cuneanes could serve as isosteric replacements of trans-1,4-disubstituted cyclohexanes and 1,3-disubstituted benzenes. An analogue of the anticancer drug sonidegib was synthesized, in which the 1,2,3-trisubstituted benzene was replaced with a 1,3-disubstituted cuneane.

Application of a Synthetic Ferredoxin-Inspired [4Fe4S]-Peptide Maquette as the Redox Partner for an [FeFe]-Hydrogenase.

'Bacterial-type' ferredoxins host a cubane [4Fe4S]2+/+ cluster that enables these proteins to mediate electron transfer and facilitate a broad range of biological processes. Peptide maquettes based on the conserved cluster-forming motif have previously been reported and used to model the ferredoxins. Herein we explore the integration of a [4Fe4S]-peptide maquette into a H2 -powered electron transport chain. While routinely formed under anaerobic conditions, we illustrate by electron paramagnetic resonance (EPR) analysis that these maquettes can be reconstituted under aerobic conditions by using photoactivated NADH to reduce the cluster at 240 K. Attempts to tune the redox properties of the iron-sulfur cluster by introducing an Fe-coordinating selenocysteine residue were also explored. To demonstrate the integration of these artificial metalloproteins into a semi-synthetic electron transport chain, we utilize a ferredoxin-inspired [4Fe4S]-peptide maquette as the redox partner in the hydrogenase-mediated oxidation of H2 .

Heteroleptic iron(ii) complexes with naphthoquinone-type ligands.

Heteroleptic iron complexes with a naphthoquinone-type ligand, 2-(pyridin-2-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione (HL), were synthesized, and their structures and magnetic properties were investigated. Two spin-crossover complexes, [Fe(L)2(L1)] (1, L1 = ethylenediamine) and [Fe(L)2(L2)] (2, L2 = cyclohexanediamine) were structurally characterized at 100 K and 270 K, and their gradual spin crossover behavior observed by magnetic susceptibility measurements and confirmed by Mössbauer spectroscopic analyses. Two homologous iron(ii) complexes, [Fe(L)2(L3c)] (3, L3c = diimino benzoquinone) and [Fe(L)2(L4c)] (4, L4c = iminosuccinonitrile), were found to exist in the low-spin state in the range of 10-300 K. In contrast, the corresponding complex with two water ligands, [Fe(L)2(H2O)2] (5), and the tris-chelate complex with protonated ligands (HL), [Fe(HL)3](BF4)2 (6), were found to be high-spin.

A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States.

A mononuclear FeII complex, prepared with a Brønsted diacid ligand, H2 L (H2 L=2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [FeII (H2 L)2 ](BF4 )2 (1A ), exhibits abrupt spin transition at T1/2 =258 K, and treatment with base yields a deprotonated analogue [FeII (HL)2 ] (1B ), which shows gradual SCO above 350 K. A range of FeIII analogues were also characterized. [FeIII (HL)(H2 L)](BF4 )Cl (1C ) has an S=5/2 spin state, while the deprotonated complexes [FeIII (L)(HL)], (1D ), and (TEA)[FeIII (L)2 ], (1E ) exist in the low-spin S=1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices.

Carboxylic Acid Functionalized Spin-Crossover Iron(II) Grids for Tunable Switching and Hybrid Electrode Fabrication.

Two carboxyl-substituted iron(II) grids, one protonated, [Fe4(HL)4](BF4)4·4MeCN·AcOEt (1), and the other deprotonated, [Fe4(L)4]·DMSO·EtOH (2), where H2L = 4-{4,5-bis[6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl]-1 H-imidazol-2-yl}benzoic acid, were synthesized. Single-crystal X-ray structure analyses reveal that both complexes have a tetranuclear [2 × 2] grid structure. 1 formed one-dimensional chains through intermolecular hydrogen bonds between the carboxylic acid units of neighboring grids, while 2 formed two-dimensional layers stabilized by π-π-stacking interactions. 1 showed spin transition between the 3HS-1LS and 1.5HS-2.5LS states around 200 K, while 2 showed spin-crossover between the 4LS and 2LS-2HS states above 300 K. A modified indium-tin oxide (ITO) electrode was fabricated by soaking the ITO in a solution of 1. The resultant electrode showed reversible redox waves attributed to the original redox processes of iron(II)/iron(III).

Two-electron redox-active tricyano iron(ii) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as a building block for coordination polymers.

A new tricyano iron(ii) building unit, [{K(H2O)4}{FeII(CN)3(L)}]·3H2O (1), was synthesized by the reaction of Moor's salts with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (L) as a capping ligand. X-ray structural analysis reveals that the mononuclear iron(ii) tricyano complex consists of one ligand and three cyanide groups, with K+ ions coordinated between neighboring units to form a one-dimensional chain network structure. 1 shows two reversible redox waves at +0.713 and -0.849 V vs. SCE, which are assigned as Fe(ii)/Fe(iii) and L/L˙- processes, respectively. One-dimensional 4,2-ribbon chain type coordination polymers, [MII(H2O)2{FeII(CN)3(L)}2]·6H2O (M = Fe (2) and Mn (3)), were synthesized by using 1 as a building unit. Cryomagnetic studies reveals that 2 and 3 show paramagnetic behaviour of S = 2 and 5/2, respectively. On the other hand, reaction of 1 and Gd(NO3)3·6H2O forms another one-dimensional chain, [GdIII(NO3)2(H2O)3{FeII(CN)3(L)}]·0.5H2O·2CH3OH (4), showing S = 7/2 paramagnetic behaviour.

Cyanide-bridged decanuclear cobalt-iron cage.

A cyanide-bridged decanuclear [Co6Fe4] cluster was synthesized by a one-pot reaction, and the magnetic properties and electronic configuration were investigated. The complex displayed thermally controlled electron-transfer-coupled spin transition (ETCST) behavior between Co(III) low-spin-NC-Fe(II) low-spin and Co(II) high-spin-NC-Fe(III) low-spin states, as confirmed by single-crystal X-ray, magnetic, and Mössbauer analyses.

Programmable spin-state switching in a mixed-valence spin-crossover iron grid.

Photo-switchable systems, such as discrete spin-crossover complexes and bulk iron-cobalt Prussian blue analogues, exhibit, at a given temperature, a bistability between low- and high-spin states, allowing the storage of binary data. Grouping different bistable chromophores in a molecular framework was postulated to generate a complex that could be site-selectively excited to access multiple electronic states under identical conditions. Here we report the synthesis and the thermal and light-induced phase transitions of a tetranuclear iron(II) grid-like complex and its two-electron oxidized equivalent. The heterovalent grid is thermally inactive but the spin states of its constituent metal ions are selectively switched using different laser stimuli, allowing the molecule to exist in three discrete phases. Site-selective photo-excitation, herein enabling one molecule to process ternary data, may have major ramifications in the development of future molecular memory storage technologies.

Triple-stranded ferric helices: a π-π interaction-driven structural hierarchy of Fe5, Fe7, and Fe17 clusters.

Three polypyridine ligand-supported multinuclear iron complexes, [Fe5], [Fe7] and [Fe17], were synthesized and their physical properties were investigated. The complexes had triple-stranded helical structures with pseudo threefold symmetry, and were stabilized by varying degrees of intramolecular π-π stacking. The pentanuclear iron complex consisted of two Fe(II) and three Fe(III) ions, supported by three ligands, while the heptanuclear complex comprised four Fe(II) centres, three Fe(III) ions, and six ligands, and the heptadecanuclear complex contained seventeen Fe(III) ions and nine ligands. Electrochemical studies revealed that the pentanuclear and heptanuclear iron complexes showed pseudo-reversible three- and five-step redox behaviours, respectively. Magnetic measurements conducted on the pentanuclear and heptanuclear complexes revealed that antiferromagnetic interactions were operative between neighbouring iron ions through the oxo- and pyrazole-bridges.

Stepwise replacement of nickel with cobalt ions in a [Ni6] cluster.

Polydentate ligands were used to support planar methoxo-bridged {Ni(6-x)Co(x)} (x = 0, 1 or 2) clusters which were structurally characterized by single crystal analyses. The homometallic {Ni6} complex displayed overall ferrimagnetic interactions between metal centres, and increasing the cobalt content led to a proportional increase in ac-response.