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Library generation experiments are a key part of the discovery of new materials, methods, and models in chemistry, but the question of how to generate high quality libraries to enable discovery is nontrivial. Herein, we use coordination chemistry to demonstrate the automation of many of the workflows used for library generation in automated hardware including the Chemputer. First, we explore the target-oriented synthesis of three influential coordination complexes, to validate key synthetic operations in our system; second, the generation of focused libraries in chemical and process space; and third, the development of a new workflow for prospecting library formation. This involved Bayesian optimization using a Gaussian process as surrogate model combined with a metric for novelty (or serendipity) quantification based on mass spectrometry data. In this way, we show directed exploration of a process space toward those areas with rarer observations and build a picture of the diversity in product distributions present across the space. We show that this effectively "engineers" serendipity into our search through the unexpected appearance of acetic anhydride, formed in situ, and solvent degradation products as ligands in an isolable series of three Co(III) anhydride complexes.
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Polyoxopalladates (POPs) are a class of self-assembling palladium-oxide clusters that span a variety of sizes, shapes and compositions. The largest of this family, {Pd84 }Ac , is constructed from 14 building units of {Pd6 } and lined on the inner and outer torus by 28 acetate ligands. Due to its high water solubility, large hydrophobic cavity and distinct 1 Hâ NMR fingerprint {Pd84 }Ac is an ideal molecule for exploring supramolecular behaviour with small organic molecules in aqueous media. Molecular visualisation studies highlighted potential binding sites between {Pd84 }Ac and these species. Nuclear Magnetic Resonance (NMR) techniques, including 1 Hâ NMR, 1 H Diffusion Ordered Spectroscopy (DOSY) and Nuclear Overhauser Spectroscopy (NOESY), were employed to study the supramolecular chemistry of this system. Here, we provide conclusive evidence that {Pd84 }Ac forms a 1 : 7 host-guest complex with benzyl viologen (BV2+ ) in aqueous solution.
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Água , Água/química , Espectroscopia de Ressonância Magnética/métodosRESUMO
The assembly of nanoscale polyoxometalate (POM) clusters has been dominated by the highly reduced icosahedral {Mo132 } "browns" and the toroidal {Mo154 } "blues" which are 45 % and 18 % reduced, respectively. We hypothesised that there is space for a greater diversity of structures in this immediate reduction zone. Here we show it is possible to make highly reduced mix-valence POMs by presenting new classes of polyoxomolybdates: [MoV 52 MoVI 12 H26 O200 ]42- {Mo64 } and [MoV 40 MoVI 30 H30 O215 ]20- {Mo70 }, 81 % and 57 % reduced, respectively. The {Mo64 } cluster archetype has a super-cube structure and is composed of five different types of building blocks, each arranged in overlayed Archimedean or Platonic polyhedra. The {Mo70 } cluster comprises five tripodal {MoV 6 } and five tetrahedral {MoV 2 MoVI 2 } building blocks alternatively linked to form a loop with a pentagonal star topology. We also show how the reaction yielding the {Mo64 } super-cube can be used in the enrichment of lanthanides which exploit the differences in selectivity in the self-assembly of the polyoxometalates.
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Giant polyoxomolybdates are traditionally synthesized by chemical reduction of molybdate in aqueous solutions, generating complex nanostructures such as the highly symmetrical spherical {Mo102} and {Mo132}, ring-shaped {Mo154} and {Mo176}, and the gigantic protein sized {Mo368}, which combines both positive and negative curvature. These complex polyoxometalates are known to be highly sensitive to reaction conditions and are often difficult to reproduce, especially {Mo368}, which is often produced in yields far below 1%, meaning further investigation has always been limited. While the electrochemical properties of these materials have been studied, their electrochemical synthesis has not been explored. Herein, we demonstrate an alternative reliable synthetic method by means of electrochemistry. By using electrochemical synthesis, we have shown the synthesis of various reported polyoxomolybdates, along with some unreported structures with unique features that have yet to be reported by traditional synthetic methods. The six different giant polyoxomolybdates that were obtained via electrochemical synthesis range from the spherical {Mo102-xFex} and {Mo132} to the ring-shaped {Mo148} and {Mo154-x}, as well as the largest known polyoxometalate {Mo368}, with improved yield (up to 26.1% for {Mo368}), increased reproducibility, and shorter crystallization time compared to chemical reduction methods.
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Determining the relative configuration or enantiomeric excess of a substance may be achieved using NMR spectroscopy by employing chiral shift reagents (CSRs). Such reagents interact noncovalently with the chiral solute, resulting in each chiral form experiencing different magnetic anisotropy; this is then reflected in their NMR spectra. The Keplerate polyoxometalate (POM) is a molybdenum-based, water-soluble, discrete inorganic structure with a pore-accessible inner cavity, decorated by differentiable ligands. Through ligand exchange from the self-assembled nanostructure, a set of chiral Keplerate host molecules has been synthesised. By exploiting the interactions of analyte molecules at the surface pores, the relative configuration of chiral amino alcohol guests (phenylalaninol and 2-amino-1-phenylethanol) in aqueous solvent was establish and their enantiomeric excess was determined by 1 H NMR using shifts of ΔΔδ=0.06â ppm. The use of POMs as chiral shift reagents represents an application of a class that is yet to be well established and opens avenues into aqueous host-guest chemistry with self-assembled recognition agents.
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Amino Álcoois , Água , Cápsulas , Óxidos , EstereoisomerismoRESUMO
Metal-catalyzed C-N cross-coupling generally forms C-N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C-N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C-N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2 ) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
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Polyoxometalate molybdenum blue (MB) complexes typically exist as discrete multianionic clusters and are composed of repeating Mo building units. MB wheels such as {Mo176} and {Mo154} are made from pentagon-centered {Mo8} building blocks joined by equal number of {Mo1} units as loin, and {Mo2} dimer units as skirt along the ring edge, with the ring sizes of the MB wheels modulated by the {Mo2} units. Herein we report a new class of contracted lanthanide-doped MB structures that have replaced all the {Mo2} units with lanthanide ions on the inner rim, giving the general formula {Mo90Ln10}. We show three examples of this new decameric {Mo90Ln10} (Ln = La, Ce, and Pr) framework synthesized by high temperature reduction and demonstrate that later Ln ions result in {Mo92Ln9} (Ln = Nd, Sm), conserving one {Mo2} linker unit in its structure, as a consequence of the lanthanide contraction. Remarkably the {Mo90Ln10} compounds are the first examples of charge-neutral molybdate wheels as confirmed by BVS, solubility experiments, and redox titrations. We detail our full synthetic optimization for the isolation of these clusters and complete characterization by X-ray, TGA, UV-vis, and ICP studies. Finally, we show that this fine-tuned self-assembly process can be utilized to selectively enrich Ln-MB wheels for effective separation of lanthanides.
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Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li-U24, Li-U28, K-U28, Li/K-U60, Mo132, and Mo154, in terms of three components: enthalpy of dissolution (ΔHdiss), enthalpy of formation of aqueous POMs (ΔHf,(aq)), and enthalpy of formation of POM crystals (ΔHf,(c)). ΔHdiss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔHf,(aq) and are more stable than those containing only peroxide bridges. In general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔHf,(aq) can be accurately estimated using only ΔHf,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.
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We present a chemical discovery robot for the efficient and reliable discovery of supramolecular architectures through the exploration of a huge reaction space exceeding ten billion combinations. The system was designed to search for areas of reactivity found through autonomous selection of the reagent types, amounts, and reaction conditions aiming for combinations that are reactive. The process consists of two parts where reagents are mixed together, choosing from one type of aldehyde, one amine and one azide (from a possible family of two amines, two aldehydes and four azides) with different volumes, ratios, reaction times, and temperatures, whereby the reagents are passed through a copper coil reactor. Next, either cobalt or iron is added, again from a large number of possible quantities. The reactivity was determined by evaluating differences in pH, UV-Vis, and mass spectra before and after the search was started. The algorithm was focused on the exploration of interesting regions, as defined by the outputs from the sensors, and this led to the discovery of a range of 1-benzyl-(1,2,3-triazol-4-yl)-N-alkyl-(2-pyridinemethanimine) ligands and new complexes: [Fe(L1 )2 ](ClO4 )2 (1); [Fe(L2 )2 ](ClO4 )2 (2); [Co2 (L3 )2 ](ClO4 )4 (3); [Fe2 (L3 )2 ](ClO4 )4 (4), which were crystallised and their structure confirmed by single-crystal X-ray diffraction determination, as well as a range of new supramolecular clusters discovered in solution using high-resolution mass spectrometry.
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The controlled manipulation of the axial oxo and equatorial halide ligands in the uranyl dipyrrin complex, UO2Cl(L), allows the uranyl reduction potential to be shifted by 1.53 V into the range accessible to naturally occurring reductants that are present during uranium remediation and storage processes. Abstraction of the equatorial halide ligand to form the uranyl cation causes a 780 mV positive shift in the UV/UIV reduction potential. Borane functionalization of the axial oxo groups causes the spontaneous homolysis of the equatorial U-Cl bond and a further 750 mV shift of this potential. The combined effect of chloride loss and borane coordination to the oxo groups allows reduction of UVI to UIV by H2 or other very mild reductants such as Cp*2Fe. The reduction with H2 is accompanied by a B-C bond cleavage process in the oxo-coordinated borane.
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Molecules containing actinide-nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and for their potential for the catalytic activation of inert hydrocarbon C-H bonds. Complexes with up to three uranium-nitrogen double bonds are now being widely studied, yet those with one thorium-nitrogen double bond are rare, and those with two are unknown. A new, simple mono(imido) thorium complex and the first bis(imido) thorium complex, K[Th(âNAr)Nâ³3] and K2[Th(âNAr)2Nâ³2], are readily made from insertion reactions (Ar = aryl, Nâ³ = N(SiMe3)2) into the Th-C bond of the cyclometalated thorium amides [ThNâ³2(N(SiMe3)(SiMe2CH2))] and K[ThNâ³(N(SiMe3)(SiMe2CH2))2]. X-ray and computational structural analyses show a "transition-metal-like" cis-bis(imido) geometry and polarized ThâN bonds with twice the Wiberg bond order of the formally single Th-N bond in the same molecule.
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Complexes formed between the heaviest and lightest elements in the periodic table yield the f-block hydrides, a unique class of compounds with wide-ranging utility and interest, from catalysis to light-responsive materials and nuclear waste storage. Recent developments in syntheses and analytics, such as exploiting low-oxidation state metal ions and improvements in X-ray diffraction tools, have transformed our ability to understand, access and manipulate these important species. This perspective brings together insights from binary metal hydrides, with molecular solution phase studies on heteroleptic complexes and gas phase investigations. It aims to provide an overview of how the f-element influences hydride formation, structure and reactivity including the sometimes-surprising power of co-ligands to tune their behaviour towards a variety of applications.
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Due to the increasing energy density demands of battery technology, it is vital to develop electrolytes with high electron storage capacity. Polyoxometalate (POM) clusters can act as electron sponges, storing and releasing multiple electrons and have potential as electron storage electrolytes for flow batteries. Despite this rational design of clusters for high storage ability can not yet be achieved as little is known about the features influencing storage ability. Here we report that the large POM clusters, {P5W30} and {P8W48}, can store up to 23 e- and 28 e- per cluster in acidic aqueous solution, respectively. Our investigations reveal key structural and speciation factors influencing the improved behaviour of these POMs over those previously reported (P2W18). We show, using NMR and MS, that for these polyoxotungstates hydrolysis equilibria for the different tungstate salts is key to explaining unexpected storage trends while the performance limit for {P5W30} and {P8W48}, can be attributed to unavoidable hydrogen generation, evidenced by GC. NMR spectroscopy, in combination with the MS analysis, provided experimental evidence for a cation/proton exchange process during the reduction/reoxidation process of {P5W30} which likely occurs due to this hydrogen generation. Our study offers a deeper understanding of the factors affecting the electron storage ability of POMs and provides insights allowing for further development of these materials for energy storage.
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A number of new charge-neutral zwitterionic tris(methimazolyl)borate ligands have been synthesized, either by substitution of the dimethylamine group in the adduct (dimethylamine)tris(methimazolyl)borane (1) or by insertion into its B-N(dimethylamine) bond by an unsaturated Lewis base. Two new anionic ligands, (thiocyanato)tris(methimazolyl)borate and (cyano)tris(methimazolyl)borate, have also been accessed by this method.
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The explosion in the use of machine learning for automated chemical reaction optimization is gathering pace. However, the lack of a standard architecture that connects the concept of chemical transformations universally to software and hardware provides a barrier to using the results of these optimizations and could cause the loss of relevant data and prevent reactions from being reproducible or unexpected findings verifiable or explainable. In this Perspective, we describe how the development of the field of digital chemistry or chemputation, that is the universal code-enabled control of chemical reactions using a standard language and ontology, will remove these barriers allowing users to focus on the chemistry and plug in algorithms according to the problem space to be explored or unit function to be optimized. We describe a standard hardware (the chemical processing programming architecture-the ChemPU) to encompass all chemical synthesis, an approach which unifies all chemistry automation strategies, from solid-phase peptide synthesis, to HTE flow chemistry platforms, while at the same time establishing a publication standard so that researchers can exchange chemical code (χDL) to ensure reproducibility and interoperability. Not only can a vast range of different chemistries be plugged into the hardware, but the ever-expanding developments in software and algorithms can also be accommodated. These technologies, when combined will allow chemistry, or chemputation, to follow computation-that is the running of code across many different types of capable hardware to get the same result every time with a low error rate.
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A family of six polyoxometalate-based magnetic compounds were synthesized by anchoring N-oxide type TEMPO radicals onto an Anderson type polyoxometalate cluster. The complexes were structurally characterised by single crystal X-ray diffraction and the intramolecular paramagnetic interactions between TEMPO radicals and Mn ions of the resulting hybrids were investigated in detail by electron paramagnetic resonance and the Evans NMR method.
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Eight alkene-functionalized molybdenum-based spherical Keplerate-type (inorganic fullerene) structures have been obtained via both direct and multistep synthetic approaches. Driven by the opportunity to design unique host-guest interactions within hydrophobic, π-electron rich confined environments, we have synthesised {(NH4)42[Mo132O372(L)30(H2O)72]}, where L = (1) acrylic acid, (2) crotonic acid, (3) methacrylic acid, (4) tiglic acid, (5) 3-butenoic acid, (6) 4-pentenoic acid, (7) 5-hexenoic acid, and (8) sorbic acid. The compounds, which are obtained in good yield (10-40%), contain 30 carboxylate-coordinated alkene ligands which create a central cavity with hydrophobic character. Extensive Nuclear Magnetic Resonance (NMR) spectroscopy studies contribute significantly to the complete characterisation of the structures obtained, including both 1D and 2D measurements. In addition, single-crystal X-ray crystallography and subsequently-generated electron density maps are employed to highlight the distribution in ligand tail positions. These alkene-containing structures are shown to effectively encapsulate small alkyl thiols (1-propanethiol (A), 2-propanethiol (B), 1-butanethiol (C), 2-butanethiol (D) and 2-methyl-1-propanethiol (E)) as guests within the central cavity in aqueous solution. The hydrophobically driven clustering of up to 6 equivalents of volatile thiol guests within the central cavity of the Keplerate-type structure results in effective thermal protection, preventing evaporation at elevated temperatures (ΔT ≈ 25 K).
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The exploration of complex multicomponent chemical reactions leading to new clusters, where discovery requires both molecular self-assembly and crystallization, is a major challenge. This is because the systematic approach required for an experimental search is limited when the number of parameters in a chemical space becomes too large, restricting both exploration and reproducibility. Herein, we present a synthetic strategy to systematically search a very large set of potential reactions, using an inexpensive, high-throughput platform that is modular in terms of both hardware and software and is capable of running multiple reactions with in-line analysis, for the automation of inorganic and materials chemistry. The platform has been used to explore several inorganic chemical spaces to discover new and reproduce known tungsten-based, mixed transition-metal polyoxometalate clusters, giving a digital code that allows the easy repeat synthesis of the clusters. Among the many species identified in this work, the most significant is the discovery of a novel, purely inorganic W24FeIII-superoxide cluster formed under ambient conditions. The modular wheel platform was employed to undertake two chemical space explorations, producing compounds 1-4: (C2H8N)10Na2[H6Fe(O2)W24O82] (1, {W24Fe}), (C2H8N)72Na16[H16Co8W200O660(H2O)40] (2, {W200Co8}), (C2H8N)72Na16[H16Ni8W200O660(H2O)40] (3, {W200Ni8}), and (C2H8N)14[H26W34V4O130] (4, {W34V4}), along with many other known species, such as simple Keggin clusters and 1D {W11M2+} chains.
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The precise control over the formation of complex nanostructures, e.g. polyoxometalates (POMs), at the sub-nanoscale is challenging but critical if non-covalent architectures are to be designed. Combining biologically-evolved systems with inorganic nanostructures could lead to sequence-mediated assembly. Herein, we exploit oligopeptides as multidentate structure-directing ligands via metal-coordination and hydrogen bonded interactions to modulate the self-assembly of POM superstructures. Six oligopeptides (GH, AH, SH, G2H, G4H and G5H) are incorporated into the cavities of Molybdenum Blue (MB) POM nanowheels. It is found that the helicity of the nanowheel can be readily switched (Δ to Λ) by simply altering the N-terminal amino acid on the peptide chain rather than their overall stereochemistry. We also reveal a delicate balance between the Mo-coordination and the hydrogen bonds found within the internal cavity of the inorganic nanowheels which results in the sequence mediated formation of two unprecedented asymmetrical nanowheel frameworks: {Mo122Ce5} and {Mo126Ce4}.
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The uranyl(vi) complex UO2Cl(L) of the redox-active, acyclic diimino-dipyrrin anion, L- is reported and its reaction with inner- and outer-sphere reductants studied. Voltammetric, EPR-spectroscopic and X-ray crystallographic studies show that chemical reduction by the outer-sphere reagent CoCp2 initially reduces the ligand to a dipyrrin radical, and imply that a second equivalent of CoCp2 reduces the U(vi) centre to form U(v). Cyclic voltammetry indicates that further outer-sphere reduction to form the putative U(iv) trianion only occurs at strongly cathodic potentials. The initial reduction of the dipyrrin ligand is supported by emission spectra, X-ray crystallography, and DFT; the latter also shows that these outer-sphere reactions are exergonic and proceed through sequential, one-electron steps. Reduction by the inner-sphere reductant [TiCp2Cl]2 is also likely to result in ligand reduction in the first instance but, in contrast to the outer-sphere case, reduction of the uranium centre becomes much more favoured, allowing the formation of a crystallographically characterised, doubly-titanated U(iv) complex. In the case of inner-sphere reduction only, ligand-to-metal electron-transfer is thermodynamically driven by coordination of Lewis-acidic Ti(iv) to the uranyl oxo, and is energetically preferable over the disproportionation of U(v). Overall, the involvement of the redox-active dipyrrin ligand in the reduction chemistry of UO2Cl(L) is inherent to both inner- and outer-sphere reduction mechanisms, providing a new route to accessing a variety of U(vi), U(v), and U(iv) complexes.