Evolution of 14-Connected Zr₆ Secondary Building Units through Postsynthetic Linker Incorporation

Two new zirconium MOFs, WSU-6 and WSU-7, were synthesized through postsynthetic modifications. In both cases, linker insertion was conducted on a MOF consisting of eight-connected (8-c) Zr6 cluster and four-connected (4-c) ETTC linker, WSU-5, which possesses the uncommon 4, 8-c scu-c topology. The insertion of 1, 4-benzenedicarboxylate into the MOF formed the new 4, 12-c mjh topology, WSU-6. Interestingly, when 2, 6-naphthalenedicarboxylate was inserted, WSU-7 can be formed, which possesses a new 4, 14-c jkz topology. WSU-7 contains very rare 14-c Zr6 secondary building units (SBUs) and is the first MOF to have a Zr6 SBUs with connectivity greater than 12. The three Zr-MOFs were structurally characterized, and the photoluminescence properties of the materials were also studied.