Building Conjugated Donor–Acceptor Cross-Links into Metal–Organic Frameworks for Photo- and Electroactivity

We convert a coordination network into a covalent solid, while maintaining the crystallinity and greatly enhancing the framework rigidity and redox-active and photochemical properties. Specifically, intensely light-absorbing push–pull functions are postsynthetically installed by reacting the electrophilic TCNE (tetracyanoethylene) guests and the electron-rich alkyne side arms on a microporous Zr–organic framework, generating black microporous crystallites with a band gap smaller than 1.0 eV. The reaction proceeds in the known [2 + 2] cycloaddition–retroelectrocyclization mechanism and extensively establishes conjugated (polyene) bridges across the linker molecules. The donor (4-methoxyphenyl) and acceptor (dicyanovinyl) couples of the polyene bridges also act as an efficient fluorescent quencher and can be selectively installed in a thin outer layer of the host crystallite to form a core–shell assembly for turn-on fluorescent sensing of small amine molecules in water solutions.