The cobalt bis(dicarbollide)(1⁻) anion (1⁻), [(1,2-C₂B₉H₁₁)₂-3,3′-Co(III)](1⁻), plays an increasingly important role in material science and medicine due to its high chemical stability, 3D shape, aromaticity, diamagnetic character, ability to penetrate cells, and low cytotoxicity. A key factor enabling the incorporation of this ion into larger organic molecules, biomolecules, and materials, as well as its capacity for “tuning” interactions with therapeutic targets, is the availability of synthetic routes that enable easy modifications with a wide selection of functional groups. Regarding the modification of the dicarbollide cage, syntheses leading to substitutions on boron atoms are better established. These methods primarily involve ring cleavage of the ether rings in species containing an oxonium oxygen atom connected to the B(8) site. These pathways are accessible with a broad range of nucleophiles. In contrast, the chemistry on carbon vertices has remained less elaborated over the previous decades due to a lack of reliable methods that permit direct and straightforward cage modifications. In this review, we present a survey of methods based on metalation reactions on the acidic C-H vertices, followed by reactions with electrophiles, which have gained importance in only the last decade. These methods now represent the primary trends in the modifications of cage carbon atoms. We discuss the scope of currently available approaches, along with the stereochemistry of reactions, chirality of some products, available types of functional groups, and their applications in designing unconventional drugs. This content is complemented with a report of the progress in physicochemical and biological studies on the parent cobalt bis(dicarbollide) ion and also includes an overview of recent syntheses and emerging applications of boron-substituted compounds.

Rare-earth elements (REEs) are critical materials in modern industry, but their production has a significant environmental footprint. Environmentally friendly separation methods would enable efficient, sustainable recycling of REEs. This work introduces a class of cyclen-based macrocyclic chelators that induce significant differences in solubility for REE chelates, enabling their selective precipitation from pH-neutral aqueous solution. The process was refined using simple coordinating additives (e.g., acetate) to form ternary coordination compounds to fine-tune these chelate solubilities. Conditions were optimized for the REEs found in NdFeB magnets, allowing separations of even adjacent lanthanides by repeated precipitations. Separation factors comparable to those of industrial solvent extraction methods were achieved without organic solvents. Analysis of NdFeB magnets from current electric car motors revealed an unexpected presence of holmium as a supplement and/or replacement for terbium and dysprosium, suggesting shifting industrial trends with implications for future recycling efforts. In a case study, one such automotive magnet was processed to obtain a 99.7% pure neodymium product. Scalable, tunable, and entirely aqueous, this approach advances the sustainable use of REEs toward a circular economy.

Platinum compounds remain the first-line drugs for the treatment of most lethal gynecological malignancies and ovarian cancers. Acquired platinum resistance remains a major challenge in gynecological oncology. Considering the unique physicochemical properties of the metallacarboranes modifier and the significant role of nucleoside derivatives as anticancer antimetabolites, we designed and synthesized a set of adenosine conjugates with metallacarboranes containing iron, cobalt, or chromium as semi-abiotic compounds that influence the cisplatin sensitivity of ovarian cancer cells. Adherent cultures of ovarian carcinoma cell lines and multicellular spheroids, ranging from sensitive to highly resistant including experimental cell lines “not responding” to platinum drugs were used. Iron-containing metallacarborane conjugates showed the best anticancer activity, especially against resistant cells. Compound modified at the C2′ nucleoside position showed the best activity in resistant cancer cells and highly resistant cancer spheroids exposed to cisplatin, increasing cell cycle arrest, apoptosis or necrosis, and reactive oxygen species production. Moreover, it showed high cellular accumulation and did not induce cross-resistance to cisplatin, carboplatin, doxorubicin, paclitaxel, or gemcitabine in long-term cultures. The reference nido-carborane derivative (no metal ions) and unmodified nucleosides were not as effective. These findings indicate that metallacarborane modification of adenosine may sensitize ovarian cancer cells to cisplatin in combination treatment.

A series of Schiff base ligands obtained by the condensation of trans-cyclohexane-1,2-diamine and fluorinated benzaldehydes were prepared, followed by their reduction with NaBH₄. The reduced ligands were employed in the synthesis of zinc complexes of the general formula [ZnCl₂(L)]. The structures of both the original and the reduced Schiff bases, as well as of the zinc complexes, were characterized by single-crystal X-ray analysis, along with NMR and IR spectroscopy. The antimicrobial activities of the reduced Schiff bases and their zinc complexes were evaluated in vitro against E. coli, S. aureus, and C. albicans. The compounds containing the 4-(trifluoromethylphenyl) moiety showed marked antibacterial activity. Interestingly, the antimicrobial effect of the zinc complex with this moiety was significantly higher than that of the corresponding free reduced ligand, comparable with ciprofloxacin used as standard. Thus, a synergic effect upon the complexation with zinc can be inferred.

Coordination compounds of lanthanides are indispensable in biomedical applications as MRI contrast agents and radiotherapeutics. However, since the introduction of the chelator DOTA four decades ago, there has been only limited progress on improving their thermodynamic stability and kinetic inertness, which are essential for safe in vivo use. Here, we present ClickZip, an innovative synthetic strategy employing a coordination-templated formation of a 1,5-triazole bridge that improves kinetic inertness up to a million-fold relative to DOTA, expanding utility of lanthanide chelates beyond traditional uses. Acting as unique mass tags, the ClickZip chelates can be released from (biological) samples by acidic hydrolysis, chromatographically distinguished from interfering lanthanide species, and sensitively detected by mass spectrometry. Lanthanides enclosed in ClickZip chelates are chemically almost indistinguishable, providing a more versatile alternative to chemically identical isotopic labels for multiplexed analysis. The bioanalytical potential is demonstrated on tagged cell-penetrating peptides in vitro, and anti-obesity prolactin-releasing peptides in vivo.