Two different conjugated microporous polymers (CMPs) based on tetrakis(4-ethynylphenyl)stannane as the repeating unit were synthesized and their BET surfaces and thermal properties were investigated. The first direct method to elucidate the molecular structure of the organic linkers between the tin centers by digestion of the CMP is described. Selective cleavage of the tin-carbon bonds with chloroacetic acid afforded the isolated bridging units and provided insight into the surprisingly varied chemical composition of these networks.

We synthesized conjugated microporous polymers (CMPs) based on tetrakis(4-ethynylphenyl)stannane and diiodobenzene as tectons, using Sonogashira couplings under different conditions. Through variation of the reaction conditions (catalysts, bases and solvents), appearance, surface area and emission properties of the formed CMPs were significantly altered. Wet-chemical, acid-mediated digestion and analysis of the resulting struts of these otherwise insoluble networks give insight into the molecular setup.

Three Sonogashira–Hagihara polymerization protocols were applied for the synthesis of conjugated microporous polymers (CMPs) by using group IV tetra(p‐ethynylphenyl) monomers with 1,4‐diiodobenzene or 1,4‐dibromobenzene. The optical properties and surface areas of the CMPs were compared and related to the preparation conditions and the geometry of the tetrahedral building block as obtained after X‐ray analysis. In each series, surface areas decreased—independently from the chosen parameters of catalyst, base, and solvent—from carbon‐centered CMPs (1595 m2 g−1) to silicon‐, germanium‐, and tin‐centered (649 m2 g−1) networks.

Arylated butadienes were prepared employing transition-metal coupling techniques and characterized via UV/vis spectroscopy and X-ray crystal structure analysis. Identification of byproducts led to a photochemical route toward novel multiarylated dihydronaphthalenes. Arylbutadiene-dihydronaphthalene cyclization occurs in solution and in the solid state. Upon substitution of hexaphenylbutadiene, absorption is red-shifted and stability under ambient light is even more reduced.

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