Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

Abstract

Icosahedral boranes, carboranes, and metallacarboranes are extraordinarily robust compounds with desirable properties such as thermal and redox stability, chemical inertness, low nucleophilicity, and high hydrophobicity, making them attractive for several applications such as medicine, nanomaterials, molecular electronics, energy, catalysis, environmental chemistry, and other areas. The hydrogen atoms in these clusters can be replaced by convenient groups that open the way to a chemical alternative to conventional "organic" or "organometallic" realms. Icosahedral boron cluster derivatives have been reviewed from different perspectives; however, there is a need for a review dedicated to the redox and photophysical characteristics of easily accessible borane and carborane derivatives, which are excellent materials for a wide range of applications. This review deals with the redox properties and photoluminescence behavior of this collection of compounds, as well as their influence on the properties of materials and devices whose working principles are related to electron-transfer or electron-promotion phenomena. We hope that this review will be of great value to boron cluster scientists and researchers working in the photoluminescence and electrochemistry fields who are interested in exploring the possibilities of these unique and promising systems.

Methylsulfanyl‐Stabilized Rotamers of Cobalt Bis(dicarbollide)

“…This latter would usually be expected to be ca. 3 V more anodic than the Co III /Co II redox process, [29] whereas the oxidations of these compounds are shifted anodically by only 1.7-1.9 V with respect to the Co III /Co II change. As a consequence, the oxidation of Co III is not observed at all in these cases, as it would involve the removal of one electron from a species with a high positive charge.…”

“…1 V, as observed previously. [29] Apparently, either they do not trigger any conversion between rotamers or this is not detectable by cyclic voltammetry. On the other hand, the sulfide oxidation has some unexpected features: in contrast to ordinary sulfides and as for 1,5-dithiacyclooctane (1,5-DTCO), 1,5-dithiacyclononane (1,5-DTCN), and 1,6-dithiacyclodecane (1,6-DTCD), [30] these B-methylsulfanyl derivatives of cobaltacarborane are oxidized readily in a process with some features of chemical reversibility (on the time scale of cyclic voltammetry).…”

Synthesis and Applications of Perfunctionalized Boron Clusters

“…Contemporary books and reviews have broadly showcased recent advances in boron cluster chemistry and their applications, 7–19 but in this Viewpoint we hope to reveal to the wider inorganic chemistry community the immense potential of boron clusters by focusing on a particular class of molecules, namely perfunctionalized clusters whose cores are composed entirely of boron atoms. We will discuss their synthesis and unique attributes and then present examples of their use in some unusual and unexpected arenas, ranging from photo-activation of olefins to hybrid nanomolecules.…”

Thecloso‐Dodecaborate Dianion Fused with Oxazoles Provides 3D Diboraheterocycles with Selective Antimicrobial Activity

“…They belong to the class of closo-borohydrides, and the ones experimentally studied are the [B 12 H 12 ] 2À ,[ CB 11 H 12 ] À ,a nd C 2 B 10 H 12 clusters;t here are three {C 2 B 10 }c age isomers with carbon atoms in the 1,2-, 1,7-, and 1,12-positions, often referred to as ortho-, meta-, and para-dicarbadodecaborane (Figure 1a). They belong to the class of closo-borohydrides, and the ones experimentally studied are the [B 12 H 12 ] 2À ,[ CB 11 H 12 ] À ,a nd C 2 B 10 H 12 clusters;t here are three {C 2 B 10 }c age isomers with carbon atoms in the 1,2-, 1,7-, and 1,12-positions, often referred to as ortho-, meta-, and para-dicarbadodecaborane (Figure 1a).…”