200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the "space race" while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules-a phenomenon best described as "organomimetic". Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion.
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http://dx.doi.org/10.1351/PAC-CON-13-01-13 | DOI Listing |
J Mater Chem B
October 2024
Institut de Ciència de Materials de Barcelona (C.S.I.C.) Campus U.A.B, 08193 Bellaterra, Barcelona, Spain.
Anticancer drugs inhibit DNA replication by intercalating between DNA base pairs, forming covalent bonds with nucleotide bases, or binding to the DNA groove. To develop safer drugs, novel molecular structures with alternative binding mechanisms are essential. Stable boron hydrides offer a promising alternative for cancer therapy, opening up additional options like boron neutron capture therapy based on B and thermal neutron beams or proton boron fusion therapy using B and proton beams.
View Article and Find Full Text PDFChem Sci
July 2024
Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science and Technology 130 Meilong Road 200237 Shanghai China
Due to the expanding applications of icosahedral carboranes in medicinal and materials chemistry research, their functionalizations have become one of the central themes in boron-rich cluster chemistry. Although several strategies for incorporating nitrogen-containing nucleophiles on a single boron vertex of the icosahedral carboranes (CBH) have been developed, methods for preparing clusters with vicinal B-N moieties are still lacking. The steric bulk of icosahedral carboranes and disparate electronic and steric nature of the N-containing groups have rendered the vicinal diamination challenging.
View Article and Find Full Text PDFInorg Chem
May 2023
Chemical Information Sciences Lab, Department of Chemistry, Pondicherry University, Pondicherry 605014, India.
Polyhedral boron clusters are lauded as 3D aromatics that frequently form interconnected periodic networks resulting in boron-rich borides with metal and non-metals having high thermodynamic stability and hardness. This leads to the question of whether the spherical delocalization of electrons in these clusters is extended across the network as in organic aromatic networks. These borides also frequently show partial oxidation, having fewer electrons than what is mandated by electron counting rules, whose impact on their aromatic stability and geometry remains mysterious.
View Article and Find Full Text PDFJ Mol Model
March 2023
Nanotechnology Engineering and Materials Science and Mechanical Engineering Program, Abdullah Gül University, Kayseri, Turkey.
Context: By means of ab initio molecular dynamics simulations, possible boron-rich amorphous silicon borides (BSi, 0.5 ≤ n ≤ 0.95) are generated and their microstructure, electrical properties and mechanical characters are scrutinized in details.
View Article and Find Full Text PDFJ Mater Chem B
December 2022
Centro de Ciências e Tecnologias Nucleares and Departamento de Engenharia e Ciências Nucleares, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, 2695-066 Bobadela LRS, Portugal.
Glioblastoma multiforme (GBM) is the most common and fatal primary brain tumor, and is highly resistant to conventional radiotherapy and chemotherapy. Therefore, the development of multidrug resistance and tumor recurrence are frequent. Given the poor survival with the current treatments, new therapeutic strategies are urgently needed.
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