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<i>Closo</i> <i>m</i>-C₂B₁₀H₁₂ can perform as a novel core of globular periphery-decorated macromolecules. To do this, a new class of di and tetrabranched <i>m</i>-carborane derivatives has been synthesized by a judicious choice of the synthetic procedure, starting with 9,10-I₂-1,7-<i>closo</i>-C₂B₁₀H₁₀. The 2a-NPA (sum of the natural charges of the two bonded atoms) value for a bond, which is defined as the sum of the NPA charges of the two bonded atoms, matches the order of electrophilic reaction at the different cluster bonds of the icosahedral <i>o</i>-and <i>m</i>- carboranes that lead to the formation of B-I bonds. As for <i>m</i>-carborane, most of the 2a-NPA values of B-H vertexes are positive, and their functionalization is more challenging. The synthesis and full characterization of dibranched 9,10-R₂-1,7-<i>closo</i>-carborane (R = CH₂CHCH₂, HO(CH₂)₃, Cl(CH₂)₃, TsO(CH₂)₃, C₆H₅COO(CH₂)₃, C₆H₅COO(CH₂)₃, N₃(CH₂)₃, CH₃CHCH, and C₆H₅C₂N₃(CH₂)₃) compounds as well as the tetrabranched 9,10-R₂-1,7-R₂-<i>closo</i>-C₂B₁₀H₈ (R = CH₂CHCH₂, HO(CH₂)₃) are presented. The X-ray diffraction of 9,10-(HO(CH₂)₃)₂-1,7-<i>closo</i>-C₂B₁₀H₁₀ and 9,10-(CH₃CHCH)₂-1,7-<i>closo</i>-C₂B₁₀H₁₀, as well as their Hirshfeld surface analysis and decomposed fingerprint plots, are described. These new reported tetrabranched <i>m</i>-carborane derivatives provide a sort of novel core for the synthesis of 3D radially grown periphery-decorated macromolecules that are different to the 2D radially grown core of the tetrabranched <i>o</i>-carborane framework.