Carborane-based heteromolecular extended networks driven by directional C-Te⋯N chalcogen bonding interactions.

We demonstrate that o-closo -(TeMe) 2 carborane directs, in the presence of linear ditopic neutral Lewis bases, the formation of co-crystals with 1D extended supramolecular networks. Specifically, the network formation is systematically stabilized by short and quasi-linear C-Te⋯N chalcogen-bonding (ChB) interactions. In sum, we report efficient carborane-based tectons to rationally design high-dimensional neutral heteromolecular networks.