m-Carborane as a Novel Core for Periphery-Decorated Macromolecules

Area of Science:

• Organometallic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Meta-carborane (m-carborane) clusters serve as versatile cores for macromolecular architectures.
• Functionalization of carborane cages, particularly m-carboranes, presents synthetic challenges due to electronic properties of B-H vertices.
• Previous work focused on ortho-carborane frameworks for 2D radial growth.

Purpose of the Study:

• To synthesize novel di- and tetrabranched m-carborane derivatives.
• To explore their potential as cores for 3D radially grown macromolecules.
• To characterize the synthesized compounds and understand their structural properties.

Main Methods:

• Synthesis of di- and tetrabranched m-carborane derivatives starting from 9,10-I2-1,7-closo-C2B10H10.
• Full characterization including X-ray diffraction analysis.
• Hirshfeld surface analysis and decomposed fingerprint plots for structural insights.

Main Results:

• Successful synthesis and characterization of various dibranched (9,10-R2-1,7-closo-carborane) and tetrabranched (9,10-R2-1,7-R2-closo-C2B10H8) m-carborane derivatives.
• X-ray diffraction and Hirshfeld surface analysis provided detailed structural information for selected compounds.
• The study identified specific electronic properties (2a-NPA values) influencing electrophilic reactivity at cluster bonds.

Conclusions:

• The synthesized tetrabranched m-carborane derivatives represent a novel core structure for constructing 3D radially grown macromolecules.
• These findings offer a new avenue for designing complex macromolecular architectures with distinct growth patterns compared to o-carboranes.
• The study highlights the importance of judicious synthetic strategies and electronic property analysis in carborane chemistry.