Discovered by Stock and Pohland in 1926, borazine is the isoelectronic and isostructural inorganic analogue of benzene, where the C[double bond, length as m-dash]C bonds are substituted by B-N bonds. The strong polarity of such heteroatomic bonds widens the HOMO-LUMO gap of the molecule, imparting strong UV-emitting/absorption and electrical insulating properties. These properties make borazine and its derivatives valuable molecular scaffolds to be inserted as doping units in graphitic-based carbon materials to tailor their optoelectronic characteristics, and specifically their semiconducting properties. By guiding the reader through the most significant examples in the field, in this feature paper we describe the past and recent developments in the organic synthesis and functionalisation of borazine and its derivatives. These boosted the production of a large variety of tailored derivatives, broadening their use in optoelectronics, H2 storage and supramolecular functional architectures, to name a few.
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http://dx.doi.org/10.1039/c5cc06611e | DOI Listing |
J Am Chem Soc
December 2024
Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1, 69100 Villeurbanne, France.
A borazine derivative functionalized by nitroxide free radicals, ,',″-(tris(4-Bromophenyl))-,',″-tris((2,6-dimethyl-4-(--butyl--oxyamino)phenyl) borazine (), was synthesized as a milestone of open-shell inorganic benzene. The crystal structure determined from X-ray diffraction on a single crystal ascertains the grafting of three nitroxide radicals. The temperature dependence of the magnetic susceptibility evidences weak intramolecular antiferromagnetic interactions between the radicals with strong intermolecular antiferromagnetic interactions between two nitroxide moieties of two neighboring molecules.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
University of Vienna Faculty of Chemistry: Universitat Wien Fakultat fur Chemie, Institute of Organic Chemistry, Währinger Strasse 38, 1090, Vienna, AUSTRIA.
Borazine and its derivatives can be considered critical doping units for engineering hybrid C(sp2)-based molecules with tailored optoelectronic properties. Herein, we report the first synthesis of hexaarylborazines that, bearing ortho-substituted aryl moieties, extend three-dimensionally. Using a one-pot protocol, we first form an electrophilic chloroborazole and then react it with an aryl lithium (ArLi).
View Article and Find Full Text PDFMolecules
October 2024
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK.
Imidazo-fused diazaborines, which serve as intermediary structures somewhat alongside benzene and borazine, had been of particular interest to Dewar and Snyder more than 60 years ago. To this end, Dewar utilised his 'π-'so as to represent ''as a '' species; however, sadly, modern representations have deviated and leapt into '' counterparts. Bonding in boron species has never been straightforward, to such an extent that the orthodox '' like diborane, , HB-BH, which conformed to the paradigmatic rules of molecular structure, in particular, hybridisation and electronegativity, was later evolved to a more realistic '' bonding so as to give the lie to the purported diborane structures of X-ray diffractors.
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October 2024
Faculty of Chemistry and Chemical Engineering, Department of Chemistry, Babeș-Bolyai University, 1 M. Kogalniceanu Street, 400084 Cluj-Napoca, Romania.
The current study investigates the influence of several R substituents (e.g., Me, SiH, F, Cl, Br, OH, NH, etc.
View Article and Find Full Text PDFChemistry
December 2024
Physics Department E20, TUM School of Natural Sciences, Technical University of Munich, Garching, Germany.
The on-surface synthesis strategy has emerged as a promising route for fabricating well-defined two-dimensional (2D) BN-substituted carbon nanomaterials with tunable electronic properties. This approach relies on specially designed precursors and requires a thorough understanding of the on-surface reaction pathways. It promises precise structural control at the atomic scale, thus complementing chemical vapor deposition (CVD).
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