Comment on “Bi-functional Li2B12H12 for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye” by J. A. Teprovich Jr, H. Colón-Mercado, A. L. Washington II, P. A. Ward, S. Greenway, D. M. Missimer, H. Hartman, J. Velten, J. H. Christian and R. Zidan, J. Mater. Chem. A, 2015, 3, 22853

Paskevicius, Mark; Jakobsen, Anders S.; Bregnhøj, Mikkel; Hansen, Bettina; Møller, Kasper T.; Ogilby, Peter R.

doi:10.1039/c8ta10735a

Cited by 8 publications

(4 citation statements)

References 13 publications

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“…For example, due to their large HOMO–LUMO gaps, unfunctionalized boron clusters (e.g., closo -[B 12 H 12 ] 2– ) remain photophysically inert. Therefore, they are energetically unlikely to engage in photoexcited charge-transfer or electron-transfer behavior induced by visible light, despite some recent mechanistic claims. , We note that identification of impurities and careful and complete spectroscopic characterization is always critical to ascertain the photophysical properties of any molecular and hybrid systems containing new boron cluster species. − …”

Section: Discussionmentioning

confidence: 99%

Redox-Active Boron Clusters

Ready,

Nelson,

Torres Pomares

et al. 2024

Acc. Chem. Res.

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In this Account, we discuss our group's research over the past decade on a class of functionalized boron clusters with tunable chemical and physical properties, with an emphasis on accessing and controlling their redox behavior. These clusters can be thought of as three-dimensional aromatic systems that have distinct redox behavior and photophysical properties compared to their two-dimensional organic counterparts. Specifically, our lab has studied the highly tunable, multielectron redox behavior of B 12 (OR) 12 clusters and applied these molecules in various settings. We first discuss the spectroscopic and electrochemical characterization of B 12 (OR) 12 clusters in various oxidation states, followed by their use as catholytes and/or anolytes in redox flow batteries and chemical dopants in conjugated polymers. Additionally, the high oxidizing potential and visible light-absorbing nature of fluoroaryl-functionalized B 12 (OR) 12 clusters have been leveraged by our group to generate weakly coordinating, photoexcitable species that can promote photooxidation chemistry. We have further translated these solution-phase studies of B 12 (OR) 12 clusters to the solid state by using the precursor [B 12 (OH) 12 ] 2− cluster as a robust building block for hybrid metal oxide materials. Specifically, we have shown that the boron cluster can act as a thermally stable cross-linking material, which enhances electron transport between metal oxide nanoparticles. We applied this structural motif to create TiO 2 -and WO 3 -containing materials that showed promising properties as photocatalysts and electroactive materials for supercapacitors. Building on this concept, we later discovered that B 12 (OCH 3 ) 12 , the smallest of the B 12 (OR) 12 family, could retain its redox behavior in the solid state, a previously unseen phenomenon. We successfully harnessed this unique behavior for solid-state energy storage by implementing this boron cluster as a cathode-active material in a Li-ion prototype cell device. Recently, our group has also explored how to tune the redox properties of clusters other than B 12 (OR) 12 species by synthesizing a library of vertex-differentiated clusters containing both B-OR and B-halogen groups. Due to the additive qualities of different functional groups on the cluster, these species allow access to a region of electrochemical potentials previously inaccessible by fully substituted closo-dodecaborate alkoxy-based derivatives. Lastly, we discuss our research into smaller-sized redox-active polyhedral boranes (B 6 -and B 10 -based cluster cores). Interestingly, these clusters show significantly less redox stability and reversibility than their dodecaborate-based counterparts. While exploring the functionalization of closo-hexaborate to create fully substituted derivates (i.e., [B 6 R 6 H fac ] − ), we observed unique oxidative decomposition pathways for this cluster system. Consequently, we leveraged this oxidative instability to generate useful alkyl boronate esters via selective chemical oxidation. We furth...

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Section: Discussionmentioning

confidence: 99%

Redox-Active Boron Clusters

Ready,

Nelson,

Torres Pomares

et al. 2024

Acc. Chem. Res.

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“…A few perovskite-type metal borohydrides were investigated with respect to luminescent properties too, and it was found that CsEu(BH 4 ) 3 exhibits a 20 nm red shift compared to pristine Eu(BH 4 ) 2 [106]. Interestingly, closo-borates were also investigated regarding their photoluminescence, where ultraviolet emission was observable from Sc, Y, and La as well as Li, Na, and Eu-based B 10 H 10 2− and B 12 H 12 2− compounds, while visible light emission was postulated from arachno-borates [397].…”

Section: New Trends and Propertiesmentioning

confidence: 99%

“…Synthesis routes include wet chemistry [95,405] and especially mechano-chemistry [101,102,207,406], that can be easily scaled up, while structural investigations include the use of either x-ray or neutron diffraction and spectroscopies (e.g. Raman, NMR, FT-IR (Fourier transform infrared) etc) [158,228,[388][389][390][391][392][393][394][395][396][397][398].…”

Section: Outlooks and Conclusionmentioning

confidence: 99%

Hydrogen storage in complex hydrides: past activities and new trends

et al. 2022

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Intense literature and research efforts have focussed on the exploration of complex hydrides for energy storage applications over the past decades. A focus was dedicated to the determination of their thermodynamic and hydrogen storage properties, due to their high gravimetric and volumetric hydrogen storage capacities, but their application has been limited because of harsh working conditions for reversible hydrogen release and uptake. The present review aims at appraising the recent advances on different complex hydride systems, coming from the proficient collaborative activities in the past years from the research groups led by the experts of the Task 40 “Energy Storage and Conversion Based on Hydrogen” of the Hydrogen Technology Collaboration Programme of the International Energy Agency. An overview of materials design, synthesis, tailoring and modelling approaches, hydrogen release and uptake mechanisms and thermodynamic aspects are reviewed to define new trends and suggest new possible applications for these highly tuneable materials.

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“…32,[101][102][103] Some of the closo-hydroborate anion mixtures can also be obtained by the reaction products from [BH4] − salts and neutral decaborane B10H14. 104,105 Recent studies show that anion mixtures of closo-hydroborates or monocarbaborates with an open-cage nido-hydroborate [B11H14] − stabilize a disordered phase and also exhibit high room-temperature ionic conductivity (>10 −3 S cm −1 ) respectively . [43][44][45]68,106 In principle, Na closo-hydroborates and monocarbaborates tend to exhibit roughly one-order-of-magnitude higher conductivity upon anion mixing than Li counterparts, 32,104,107 which can be attributed to the high polarizability and large ionic radius of Na + ions that are beneficial to cation conduction in the framework of the mixed closohydroborate anions.…”

Section: Discovery Of Superionic Conductorsmentioning

confidence: 99%

Hydroborate-Based Solid Electrolytes for All-Solid-State Batteries

Asakura

Remhof

Battaglia

2022

ACS Symposium Series

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Hydroborates, i.e. ionic salts of boron-hydrogen compounds, are an emerging material class of solid electrolytes for all-solid-state batteries.In particular, some of the metal hydroborates (≠ neutral hydroboranes) featuring three-dimensional anion clusters exhibit exceptional thermal and (electro)chemical stability, and liquid-like ionic conductivity with a unique ion conduction mechanism. These characteristics enable the fabrication of competitive all-solid-state cells with stable battery cycling performance. This chapter reviews the attractive material properties of hydroborates and their implementation as highly conductive solid electrolytes in all-solid-state batteries.

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Abstract: Assessment of metal closo-borane photoluminescence.

Cited by 8 publications

References 13 publications

Redox-Active Boron Clusters

Redox-Active Boron Clusters

Hydrogen storage in complex hydrides: past activities and new trends

Hydroborate-Based Solid Electrolytes for All-Solid-State Batteries

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