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The reactions between a tetrahedrally-shaped tecton, tetrakis(4-(iodoethynyl)phenyl)methane, and tetraphenylphosphonium halides readily afford interpenetrated and densely packed diamondoid architectures sustained by C–I⋯X (X = chloride, bromide, iodide) interactions. In all these halogen-bonded networks, the halide anions act as four-connecting nodes, while the tetraphenylphosphonium cations provide essential templating information and structural support.

Graphical abstract: Diamondoid architectures from halogen-bonded halides

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