Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal-Organic Frameworks.
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Multicomponent metal-organic frameworks (MOFs) promise the precise placement of synergistic functional groups with atomic-level precision, capable of promoting fascinating developments in basic sciences and applications. However, the complexity of multicomponent systemsposesa challengetotheir structural design and synthesis. Herein, we show that linkers of low symmetry can bring new opportunities to the construction of multicomponent MOFs. A carbazole-tetracarboxylate linker of C s point group symmetry was designed and combined with an 8-connected Zr6 cluster to generate a low-symmetry MOF, PCN-609. PCN-609 contains coordinatively unsaturated Zr sites arranged within a lattice with three crystallographically distinct pockets, which can accommodate linear linkers ofdifferent lengths. Sequential linker installation was carried out to postsynthetically insert three linear linkers into PCN-609, giving rise to a quinary MOF. Functionalization of each linker from the quinary MOF system creates multivariate pore environments with unprecedented complexity.