Heterobimetallic 3d-4f complexes supported by a Schiff-base tripodal ligand.

Complexes featuring multiple metal centres are of growing interest regarding metal-metal cooperation and its tuneability. Here the synthesis and characterisation of heterobimetallic complexes of a 3d metal (4: Mn, 5: Co) and lanthanum supported by a (1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane) ligand is reported, as well as discussion of their electronic structure via electron paramagnetic resonance (EPR) spectroscopy, electrochemical experiments and computational studies. Competitive binding experiments of the ligand and various metal salts unequivocally demonstrate that in these heterobimetallic complexes the 3d metal (Mn, Co) selectively occupies the κ6-N3O3 binding site of the ligand, whilst La occupies the κ6-O6 metal binding site in line with their relative oxophilicities. EPR spectroscopy supported by density functional theory analysis indicates that the 3d metal is high spin in both cases (S = 5/2 (Mn), 3/2 (Co)). Cyclic voltammetry studies on the Mn/La and Co/La bimetallic complexes revealed a quasi-reversible Mn2+/3+ redox process and poorly-defined irreversible oxidation events respectively.

Three-Coordinate Nickel and Metal-Metal Interactions in a Heterometallic Iron-Sulfur Cluster.

Biological multielectron reactions often are performed by metalloenzymes with heterometallic sites, such as anaerobic carbon monoxide dehydrogenase (CODH), which has a nickel-iron-sulfide cubane with a possible three-coordinate nickel site. Here, we isolate the first synthetic iron-sulfur clusters having a nickel atom with only three donors, showing that this structural feature is feasible. These have a core with two tetrahedral irons, one octahedral tungsten, and a three-coordinate nickel connected by sulfide and thiolate bridges. Electron paramagnetic resonance (EPR), Mössbauer, and superconducting quantum interference device (SQUID) data are combined with density functional theory (DFT) computations to show how the electronic structure of the cluster arises from strong magnetic coupling between the Ni, Fe, and W sites. X-ray absorption spectroscopy, together with spectroscopically validated DFT analysis, suggests that the electronic structure can be described with a formal Ni1+ atom participating in a nonpolar Ni-W σ-bond. This metal-metal bond, which minimizes spin density at Ni1+, is conserved in two cluster oxidation states. Fe-W bonding is found in all clusters, in one case stabilizing a local non-Hund state at tungsten. Based on these results, we compare different M-M interactions and speculate that other heterometallic clusters, including metalloenzyme active sites, could likewise store redox equivalents and stabilize low-valent metal centers through metal-metal bonding.

Mid-infrared plasmonic filter arrays using nanoholes in gold and silver films.

Plasmonic filters based on subwavelength nanohole arrays are an attractive solution for creating arrays of filters with varying passbands in a single lithography step. In this work, we have developed a fabrication method which allows fabrication of nanohole arrays in silver by use of a thin layer of aluminum oxide, which serves the dual purpose of both capping layer and hardmask for metal patterning. We demonstrate arrays of gold and silver mid-infrared plasmonic filters, fabricated on silicon, intended for use in optical filter blocks or for future integration with infrared imagers. The filter arrays are designed for the wavelength range 2-7 µm, and exhibit peak filter transmission efficiencies around 70%.

Metal-Mediated Oligomerization Reactions of the Cyaphide Anion.

The cyaphide anion, CP- , is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) by Sm(Cp*)2 (OEt2 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl), was found to afford a tetra-metallic complex containing a 2,3-diphosphabutadiene-1,1,4,4-tetraide fragment. By contrast, non-reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3-diphosphacyclobutadiene-2,4-diide moiety. Spontaneous trimerization of Sc(Cp*)2 (CP) results in the formation of a trimetallic complex containing a 1,3,5-triphosphabenzene-2,4,6-triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.

Sulfur-Ligated [2Fe-2C] Clusters as Synthetic Model Systems for Nitrogenase.

Metal clusters featuring carbon and sulfur donors have coordination environments comparable to the active site of nitrogenase enzymes. Here, we report a series of di-iron clusters supported by the dianionic yldiide ligands, in which the Fe sites are bridged by two µ2-C atoms and four pendant S donors.The [L2Fe2] (L = {[Ph2P(S)]2C}2-) cluster is isolable in two oxidation levels, all-ferrous Fe2II and mixed-valence FeIIFeIII. The mixed-valence cluster displays two peaks in the Mössbauer spectra, indicating slow electron transfer between the two sites. The addition of the Lewis base 4-dimethylaminopyridine to the Fe2II cluster results in coordination with only one of the two Fe sites, even in the presence of an excess base. Conversely, the cluster reacts with 8 equiv of isocyanide tBuNC to give a monometallic complex featuring a new C-C bond between the ligand backbone and the isocyanide. The electronic structure descriptions of these complexes are further supported by X-ray absorption and resonant X-ray emission spectroscopies.

Mid- and long-wave infrared point spectrometer (MLPS): a miniature space-borne science instrument.

The mid- and long-wave infrared point spectrometer (MLPS) is an infrared point spectrometer that utilizes unique technologies to meet the spectral coverage, spectral sampling, and field-of-view (FOV) requirements of many future space-borne missions in a small volume with modest power consumption. MLPS simultaneously acquires high resolution mid-wave infrared (∼2-4 µm) and long-wave infrared (∼5.5-11 µm) measurements from a single, integrated instrument. The broadband response of MLPS can measure spectroscopically resolved reflected and thermally emitted radiation from a wide range of targets and return compositional, mineralogic, and thermophysical science from a single data set. We have built a prototype MLPS and performed end-to-end testing under vacuum showing that the measured spectral response and the signal-to-noise ratio (SNR) for both the mid-wave infrared (MIR) and long-wave infrared (LIR) channels of MLPS agree with established instrument models.

An Ultra-Broadband High Efficiency Polarization Beam Splitter for High Spectral Resolution Polarimetric Imaging in the Near Infrared.

A broadband, high efficiency polarized beam splitter (PBS) metagrating based on integrated resonant units (IRUs) to enable simultaneous polarization analysis, spectral dispersion, and spatial imaging in the near infrared (NIR) is developed. A PBS metagrating with a diameter of 60 mm is the key technology component of the high-resolution multiple-species atmospheric profiler in the NIR (HiMAP-NIR), which is a spaceborne instrument concept crafted to be a core payload of NASA's new generation Earth System Observatory. HiMAP-NIR will enable the aerosol profiling in Earth's planetary boundary layer (from surface to2 km altitude) by simultaneously measuring four spatial-spectral-polarimetric images from 680 to 780 nm. Through detailed optimization of hybridized resonant modes in IRUs, the PBS metagrating shows a diffraction efficiency of 70% (or better) for all four linear-polarized incident light, and polarization contrasts between orthogonal states are 0.996 (or better) from 680 to 780 nm. It meets the stringent performance required by the HiMAP-NIR exploiting a new paradigm for the broad applications of metasurfaces.

Reduction of tert-butylphosphaalkyne and trimethylsilylnitrile with magnesium(I) dimers.

We report on the reactivity of magnesium(I) dimers, [Mg(nacnac)]2 (nacnac = HC[C(Me)N(2,6-iPr2C6H3)]2 ([DippLMg]2) and HC[C(Me)N(2,4,6-Me3C6H2)]2 ([MesLMg]2)), towards the phosphaalkyne tBuCP. The steric profile of the magnesium(I) dimer results in selectivity for different products. The larger diisopropylphenyl derivative yields exclusively the monomeric dimagnesiated phosphaalkene [DippLMg]PC(tBu)([DippLMg]) (1), while the mesityl derivative facilitates reductive coupling of two phosphaalkyne equivalents to give access to the 1,3-diphosphacyclobutadienediide [MesLMg]2[(tBu)2C2P2](2). The reactivity differs in coordinating solvents such as THF, which allowed for the observation of C-P coupled products. For sake of comparison, reactions of magnesium(I) compounds with Me3SiCN were carried out. In contrast to the reactions involving tBuCP, these afforded 1,3-diazabutadienediyl complexes via reductive coupling and silyl migration processes.

Spin States, Bonding and Magnetism in Mixed-Valence Iron(0)-Iron(II) Complexes.

"Xenophilic" complexes offer metal-metal bonds between disparate metal sites, but the nature of the metal-metal bonding is often unclear. Here, we describe two novel complexes with unsupported Fe-Fe bonds, Lx Fe-Fp (LX = ß-aldiminate or ß-diketiminate; Fp = Fe(CO)2 Cp), that offer insight into Fe-Fe bonding. Mössbauer, magnetism, and DFT analysis indicate that the most accurate electronic structure description is LFeII ←Fe0 (CO)2 Cp, in which the Fe(CO)2 Cp is low-spin iron(0) and acts as an X-type ligand toward the high-spin iron(II) of the LFe fragment. This largely electrostatic interaction has a bond order of only 0.5. The three-coordinate high-spin iron(II) site has large zero-field splitting, and in addition its Mössbauer parameters can be used to rank the Fp- "metalloligand" as a donor; it is nearly as strong a donor as phosphides and alkyls.

Contrasting E-H Bond Activation Pathways of a Phosphanyl-Phosphagallene.

The reactivity of the phosphanyl-phosphagallene, [H2 C{N(Dipp)}]2 PP=Ga(Nacnac) (Nacnac=HC[C(Me)N(Dipp)]2 ; Dipp=2,6-i Pr2 C6 H3 ) towards a series of reagents possessing E-H bonds (primary amines, ammonia, water, phenylacetylene, phenylphosphine, and phenylsilane) is reported. Two contrasting reaction pathways are observed, determined by the polarity of the E-H bonds of the substrates. In the case of protic reagents (δ- E-Hδ+ ), a frustrated Lewis pair type of mechanism is operational at room temperature, in which the gallium metal centre acts as a Lewis acid and the pendant phosphanyl moiety deprotonates the substrates. Interestingly, at elevated temperatures both NH2 i Pr and ammonia can react via a second, higher energy, pathway resulting in the hydroamination of the Ga=P bond. By contrast, with hydridic reagents (δ+ E-Hδ- ), such as phenylsilane, hydroelementation of the Ga=P bond is exclusively observed, in line with the polarisation of the Si-H and Ga=P bonds.

A Cyaphide Transfer Reagent.

The cyanide ion plays a key role in a number of industrially relevant chemical processes, such as the extraction of gold and silver from low grade ores. Metal cyanide compounds were arguably some of the earliest coordination complexes studied and can be traced back to the serendipitous discovery of Prussian blue by Diesbach in 1706. By contrast, heavier cyanide analogues, such as the cyaphide ion, C≡P-, are virtually unexplored despite the enormous potential of such ions as ligands in coordination compounds and extended solids. This is ultimately due to the lack of a suitable synthesis of cyaphide salts. Herein we report the synthesis and isolation of several magnesium-cyaphido complexes by reduction of iPr3SiOCP with a magnesium(I) reagent. By analogy with Grignard reagents, these compounds can be used for the incorporation of the cyaphide ion into the coordination sphere of metals using a simple salt-metathesis protocol.

Vertical pullout tests of orchard trees for bio-inspired engineering of anchorage and foundation systems.

Application of bio-inspired design in geotechnical engineering shows promise for improving the energy and material efficiency of several processes in infrastructure construction and site characterization. This project examines tree root systems for use in future bio-inspired design to improve the capacity of foundations used to support, for example, buildings and bridges. Foundation and anchorage elements used in industry are comprised almost solely of linear elements with a constant cross-sectional geometry. This functional form has remained the same for more than a century, primarily due to material availability and installation simplicity. Knowledge and understanding of the mechanisms that contribute to capacity development of natural nonlinear or branched foundation systems, such as tree root systems, could make foundation design more sustainable. The experiments described herein show that the root systems studied are 6-10 times as efficient as a conventional micropile system in developing tensile capacity on a per volume basis, with some systems displaying nearly 100 times efficiency in comparison to a conventional shallow footings. This paper explores the relationship between root system architecture and force-displacement behavior of tree root systems to better understand how to improve foundation capacity and demonstrates the potential for a more efficient use of materials and energy as compared to conventional pile and footing approaches.

Synthesis and decarbonylation chemistry of gallium phosphaketenes.

A series of gallium phosphaketenyl complexes supported by a 1,2-bis(aryl-imino)acenaphthene ligand (Dipp-Bian) are reported. Photolysis of one such species induced decarbonylation to afford a gallium substituted diphosphene. Addition of Lewis bases, specifically trimethylphosphine and the gallium carbenoid Ga(Nacnac) (Nacnac = HC[C(Me)N-(C6H3)-2,6-iPr2]2), resulted in displacement of the phosphaketene carbonyl to yield base-stabilised phosphinidenes. In several of these transformations, the redox non-innocence of the Dipp-Bian ligand was found to give rise to radical intermediates and/or side-products.

A Phosphanyl-Phosphagallene that Functions as a Frustrated Lewis Pair.

Phosphagallenes (1 a/1 b) featuring double bonds between phosphorus and gallium were synthesized by reaction of (phosphanyl)phosphaketenes with the gallium carbenoid Ga(Nacnac) (Nacnac=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ). The stability of these species is dependent on the saturation of the phosphanyl moiety. 1 a, which bears an unsaturated phosphanyl ring, rearranges in solution to yield a spirocyclic compound (2) which contains a P=P bond. The saturated variant 1 b is stable even at elevated temperatures. 1 b behaves as a frustrated Lewis pair capable of activation of H2 and forms a 1:1 adduct with CO2 .

Linkage Isomerism Leading to Contrasting Carboboration Chemistry: Access to Three Constitutional Isomers of a Borylated Phosphaalkene.

We describe the reactivity of two linkage isomers of a boryl-phosphaethynolate, [B]OCP and [B]PCO (where [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), towards tris- (pentafluorophenyl)borane (BCF). These reactions afforded three constitutional isomers all of which contain a phosphaalkene core. [B]OCP reacts with BCF through a 1,2 carboboration reaction to afford a novel phosphaalkene, E-[B]O{(C6 F5 )2 B}C=P(C6 F5 ), which subsequently undergoes a rearrangement process involving migration of both the boryloxy and pentafluorophenyl substituents to afford Z-{(C6 F5 )2 B}(C6 F5 )C=PO[B]. By contrast, [B]PCO undergoes a 1,3-carboboration process accompanied by migration of the N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl to the carbon centre.

Synthesis of metallophosphaalkenes by reaction of organometallic nucleophiles with a phosphaethynolato-borane.

We describe the reaction of a phosphaethynolato-borane [B]OCP ([B] = N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl) with the organometallic nucleophile Na[Cp*Fe(CO)2] (Cp* = pentamethylcyclopentadienyl). The electrophilic character of [B]OCP allows for a new route towards the formation metal-phosphorus bonds affording a metallophosphaalkene that can be functionalised at both the oxygen and phosphorus atoms depending on the reagents employed.

Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene.

We report on the (tert-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through a series of stoichiometric reactions of [B]OCP with isocyanides and theoretical calculations at the Density Functional Theory (DFT) level. [B]PCO decarbonylates under photolytic conditions to afford a novel boryl-substituted diphosphene, [B]P[double bond, length as m-dash]P[B]. This reaction proceeds via a transient triplet phosphinidene which we have been able to observe spectroscopically by Electron Paramagnetic Resonance (EPR) spectroscopy.

An Isolable Phosphaethynolatoborane and Its Reactivity.

The synthesis and characterization of a stable phosphaethynolatoborane, [B]OCP (1, [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO- ) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents to afford a cyclic five-membered 6π-aromatic compound, cyclo-P2 {C[B]}O{CO[B]} (2), which decarbonylates on UV irradiation. By contrast the nickel-mediated dimerisation of 1 affords the isomeric diphosphacyclobutene [P(CO[B])]2 . When 1 is reacted with organolithium reagents such as MesLi (Mes=2,4,6-trimethylphenyl), the boryl moiety shifts and the formation of the lithoxy-boryl-phosphaalkene [LiOC[B]P(Mes)]2 was observed. The reactivity of this species towards electrophiles is also described.

Portable Remote Imaging Spectrometer coastal ocean sensor: design, characteristics, and first flight results.

The design, characteristics, and first test flight results are described of the Portable Remote Imaging Spectrometer, an airborne sensor specifically designed to address the challenges of coastal ocean remote sensing. The sensor incorporates several technologies that are demonstrated for the first time, to the best of our knowledge, in a working system in order to achieve a high performance level in terms of uniformity, signal-to-noise ratio, low polarization sensitivity, low stray light, and high spatial resolution. The instrument covers the 350-1050 nm spectral range with a 2.83 nm sampling per pixel, and a 0.88 mrad instantaneous field of view, with 608 cross-track pixels in a pushbroom configuration. Two additional infrared channels (1240 and 1610 nm) are measured by a spot radiometer housed in the same head. The spectrometer design is based on an optically fast (F/1.8) Dyson design form coupled to a wide angle two-mirror telescope in a configuration that minimizes polarization sensitivity without the use of a depolarizer. A grating with minimum polarization sensitivity and broadband efficiency was fabricated as well as a slit assembly with black (etched) silicon surface to minimize backscatter. First flight results over calibration sites as well as Monterey Bay in California have demonstrated good agreement between in situ and remotely sensed data, confirming the potential value of the sensor to the coastal ocean science community.

Astronomical demonstration of an optical vortex coronagraph.

Using an optical vortex coronagraph and simple adaptive optics techniques, we have made the first convincing demonstration of an optical vortex coronagraph that is coupled to a star gazing telescope. We suppressed by 97% the primary star of a resolvable binary system, Cor Caroli. The stars had an angular separation of 1.9lambda/D at our imaging camera. The secondary star suffered no suppression from the vortex lens.