Assembly of a Gigantic Polyoxometalate Cluster {W200Co8O660} in a Networked Reactor System

Oliva, Andreu Ruiz de la; Sans, Víctor; Miras, Haralampos N.; Yan, Jun; Zang, Hong‐Ying; Richmond, Craig J.; Long, De‐Liang; Cronin, Leroy

doi:10.1002/ange.201206572

Cited by 34 publications

(8 citation statements)

References 37 publications

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“…We have previously reported the isolation of {W200Co8} however this robotic discovery represents the first time the nickel analogue has been observed. 22 This structure requires between 4-10 weeks of crystallization time and the products are typically produced in very low yield meaning many samples containing these compounds can become contaminated with crystals of starting materials or alternative higher-yielding products. This phenomenon ranged from samples containing barely 10 crystals with up to three other products present, to vials containing {W200M8} as the sole product in relatively high yield given its rarity and size.…”

Section: Automated Inorganic Synthesismentioning

confidence: 99%

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

Salley¹,

Keenan²,

Long³

et al. 2020

Preprint

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The exploration of complex multi-component 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; modular in terms of both hardware and software, and 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 allowing the easy repeat synthesis of the clusters. Among the many species identified in this work, most significantly is the discovery of a novel, purely inorganic W24FeIII-superoxide cluster formed under ambient conditions. The Modular Wheel Platform (MWP) was then employed to undertake two chemical space explorations producing compounds [1-4]: (C2H8N)10Na2[H6Fe(O2)W24O82(H2O)25] (1, {W24Fe}), (C2H8N)72Na16[H16Co8W200O660(H2O)40] (2, {W200Co8}), (C2H8N)72Na16[H16Ni8W200 O660-(H2O)40] (3, {W200Ni8}) and (C2H8N)14[H26W34V4O130] (4, {W34V4}), along with many other known species, for example simple Keggin clusters and 1D {W11M2+} chains.

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Section: Automated Inorganic Synthesismentioning

confidence: 99%

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

Salley¹,

Keenan²,

Long³

et al. 2020

Preprint

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“…Polyoxometalates (POMs) are early d 0 transition metal polyanion clusters with wide‐ranging applications including catalysis, molecular biology and medicine, energy production and storage, and building blocks for intricate or simple functional materials. Group VI (Mo, W) yields fascinating high nuclearity POMs including {Mo 368 }, {Mo 248 }, {Mo 176 }, {W 224 }, {W 200 }, and {W 148 } that approach the size of nanoparticles, yet remain molecular in their solubility, absolute formulae and architecture, redefining the “inorganic molecule”. The rich diversity of size and topologies of these clusters is accessed through pH‐control and redox chemistry to promote rearrangement.…”

Section: Figurementioning

confidence: 99%

Strategic Capture of the {Nb₇} Polyoxometalate

Martin

Petrus

Segado

et al. 2019

Chemistry A European J

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Group V Nb‐polyoxometalate (Nb‐POM) chemistry generally lacks the elegant pH‐controlled speciation exhibited by group VI (Mo, W) POM chemistry. Here three Nb‐POM clusters were isolated and structurally characterized; [Nb14O40(O2)2H3]14−, [((UO2)(H2O))3Nb46(UO2)2O136H8(H2O)4]24−, and [(Nb7O22H2)4(UO2)7(H2O)6]22−, that effectively capture the aqueous Nb‐POM species from pH 7 to pH 10. These Nb‐POMs illustrate a reaction pathway for control over speciation that is driven by counter‐cations (Li+) rather than pH. The two reported heterometallic POMs (with UO22+ moieties) are stabilized by replacing labile H2O/HO−Nb=O with very stable O=U=O. The third isolated Nb‐POM features cis‐yl‐oxos, prior observed only in group VI POM chemistry. Moreover, with these actinide‐heterometal contributions to the burgeoning Nb‐POM family, it now transects all major metal groups of the periodic table.

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“…Also, the kinetic connections between the different cycles and sequences constitutes a minimal kinetic-genetic mechanism by which a more robust and ultimately evolvable genetic machinery may develop, and such machinery might even use an network of so-called "inorganic" reactions to start developing function (8).…”

Section: Significancementioning

confidence: 99%

Quantifying the origins of life on a planetary scale

Scharf

Cronin

2016

Proc. Natl. Acad. Sci. U.S.A.

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A simple, heuristic formula with parallels to the Drake Equation is introduced to help focus discussion on open questions for the origins of life in a planetary context. This approach indicates a number of areas where quantitative progress can be made on parameter estimation for determining origins of life probabilities, based on constraints from Bayesian approaches. We discuss a variety of "microscale" factors and their role in determining "macroscale" abiogenesis probabilities on suitable planets. We also propose that impact ejecta exchange between planets with parallel chemistries and chemical evolution could in principle amplify the development of molecular complexity and abiogenesis probabilities. This amplification could be very significant, and both bias our conclusions about abiogenesis probabilities based on the Earth and provide a major source of variance in the probability of life arising in planetary systems. We use our heuristic formula to suggest a number of observational routes for improving constraints on origins of life probabilities. T he question of whether or not life exists beyond the confines of the Earth environment is intimately related to the question of life's origins on Earth or anywhere else. For example, if just one instance of life with an independent origin is detected-whether in the solar system or on a suitable exoplanet-estimates of the Bayesian probability for life across the universe will be significantly improved. Specifically, the rate of abiogenesis per young planet could, in principle, be constrained to be at least one event per Gyr (1). Equally, if a detailed mechanism for the terrestrial origins of life (OoL) were identified and tested, a complementary estimate of the rate of planetary abiogenesis should be possible. Furthermore, the architecture of a given solar system might also lead to widely different probabilities (e.g., the proximity of Mars and Earth and their potential exchange of material might result in a fundamentally larger search space in which OoL events could occur). Discovering complex organic molecules on Mars could help elucidate this possibility (2).At present, OoL science involves a wide range of approaches, theories, and opinions. A considerable body of work now exists on hypothetical early terrestrial life and its precursor chemistry including the RNA-world hypothesis, prior polymerization chemistry, autocatalytic processes, and metabolic origins, as well as the presumed transition to fully cellular organisms. Significant work has also been undertaken on inorganic "template" chemistry, the planetary evolution of suitable material precursors, and important substrates for the emergence of a biology-including the study of electrochemical gradients in hydrothermal vents systems and processes such as serpentinization as energy sources. In addition, the genomic exploration of the modern Earth's microbial life is providing ever-deeper insight into the nature and evolution of the biosphere's nested metabolic processes (3), which may provide clues to the ori...

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Assembly of a Gigantic Polyoxometalate Cluster {W₂₀₀Co₈O₆₆₀} in a Networked Reactor System

Cited by 34 publications

References 37 publications

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

Strategic Capture of the {Nb₇} Polyoxometalate

Quantifying the origins of life on a planetary scale

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Assembly of a Gigantic Polyoxometalate Cluster {W200Co8O660} in a Networked Reactor System

Cited by 34 publications

References 37 publications

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

Strategic Capture of the {Nb7} Polyoxometalate

Quantifying the origins of life on a planetary scale

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Product

Resources

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Assembly of a Gigantic Polyoxometalate Cluster {W₂₀₀Co₈O₆₆₀} in a Networked Reactor System

Strategic Capture of the {Nb₇} Polyoxometalate