Synthesis and Applications of Perfunctionalized Boron Clusters

Axtell, Jonathan C.; Saleh, Liban M. A.; Qian, Elaine A.; Wixtrom, Alex I.; Spokoyny, Alexander M.

doi:10.1021/acs.inorgchem.7b02912

Cited by 150 publications

(129 citation statements)

References 191 publications

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“…Ionic liquids based on anionic boron clusters are promising components of electrolytes for Li‐ and Mg‐ion batteries. These ILs are replacements for volatile ethereal solvents such as tetrahydrofuran …”

Section: Borate Anions and Anionic Boron Clusters As Building Blocks mentioning

confidence: 99%

Boron: Its Role in Energy‐Related Processes and Applications

et al. 2020

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Boron's unique position in the Periodic Table, that is, at the apex of the line separating metals and nonmetals, makes it highly versatile in chemical reactions and applications. Contemporary demand for renewable and clean energy as well as energy‐efficient products has seen boron playing key roles in energy‐related research, such as 1) activating and synthesizing energy‐rich small molecules, 2) storing chemical and electrical energy, and 3) converting electrical energy into light. These applications are fundamentally associated with boron's unique characteristics, such as its electron‐deficiency and the availability of an unoccupied p orbital, which allow the formation of a myriad of compounds with a wide range of chemical and physical properties. For example, boron's ability to achieve a full octet of electrons with four covalent bonds and a negative charge has led to the synthesis of a wide variety of borate anions of high chemical and electrochemical stability—in particular, weakly coordinating anions. This Review summarizes recent advances in the study of boron compounds for energy‐related processes and applications.

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Section: Borate Anions and Anionic Boron Clusters As Building Blocks mentioning

confidence: 99%

Boron: Its Role in Energy‐Related Processes and Applications

et al. 2020

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“…[24][25][26][27][28] Certain perfunctionalized clusters of the type B 12 (OR) 12 (R = alkyl, aryl, H) behave as reversible, redox-active species with multiple accessible oxidation states. [27][28][29][30][31] Recent advances have led to the rational and rapid synthesis of such substituted dodecaboranes with tunable redox potentials. [29] We have designed a DDB cluster with a very high ground-state redox potential, which when combined with the cluster's intrinsic stabilization of electron density in its well-shielded core, makes it an outstanding candidate to molecularly dope conjugated polymers.…”

Section: Introductionmentioning

confidence: 99%

Dodecaborane‐Based Dopants Designed to Shield Anion Electrostatics Lead to Increased Carrier Mobility in a Doped Conjugated Polymer

et al. 2019

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One of the most effective ways to tune the electronic properties of conjugated polymers is to dope them with small-molecule oxidizing agents, creating holes on the polymer and molecular anions. Undesirably, strong electrostatic attraction from the anions of most dopants localize the holes created on the polymer, reducing their mobility. Here, we employ a new strategy utilizing a substituted boron cluster as a molecular dopant for conjugated polymers. By designing the cluster to have a high redox potential and steric protection of the corelocalized electron density, we obtain highly delocalized polarons with mobilities equivalent to films doped with no anions present. AC Hall effect measurements show that P3HT films doped with our boron clusters have conductivities and polaron mobilities roughly an order of magnitude higher than films doped with F 4 TCNQ, even though the boron-cluster-doped films have poor crystallinity. Moreover, the number of free carriers approximately matches the number of boron clusters, yielding a doping efficiency of ∼100%. These results suggest that shielding the polaron from the anion is a critically important aspect for producing high carrier mobility, and that the high polymer crystallinity required with dopants such as F 4 TCNQ is primarily to keep the counterions far from the polymer backbone.

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“…Dodecahydro closo-dodecaborates of transition metals (TM) have attracted interest for various applications [1,2], and have been studied in the framework of boron chemistry. As most of the compounds have been crystallized from solution they are very often prepared in solvated state [3][4][5][6][7][8][9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro closo-Dodecaborates of 3d Transition Metals and of Magnesium

et al. 2019

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Magnesium and 3d transition metals closo-borates were prepared by mechanosynthesis (ball milling) of the mixtures Na2B12H12 + MCl2 (M = Mn, Fe, Co, Ni, Mg), followed by addition of ethanol or methanol and drying under dynamic vacuum. The dead mass of NaCl is partly removed by filtration. The crystal structures of solvent-coordinated and solvent-free closo-borates have been characterized by temperature dependent synchrotron radiation X-ray powder diffraction, ab initio calculations, thermal analysis and infrared spectroscopy. Various solvated complexes containing six, four, three, two or one solvent molecules were obtained by successive removal of the solvent until in most case the solvent-free metal closo-borates were obtained with the exception of Mg whose hypothetical crystal structure, however, could have its prototype in MnB12H12. The 3d transition metal closo-borates were studied in the view of their potential use as Na- or Li-ion battery electrodes in combination with Na or Li closo-borate solid electrolytes. The metal oxidation state (II) obtained in compounds presented here does not allow such application.

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Synthesis and Applications of Perfunctionalized Boron Clusters

Cited by 150 publications

References 191 publications

Boron: Its Role in Energy‐Related Processes and Applications

Boron: Its Role in Energy‐Related Processes and Applications

Dodecaborane‐Based Dopants Designed to Shield Anion Electrostatics Lead to Increased Carrier Mobility in a Doped Conjugated Polymer

Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro closo-Dodecaborates of 3d Transition Metals and of Magnesium

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