Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production

Yingxue Diao, Nanfeng Xu, Mu Qing Li, Xunjin Zhu*, Zhengtao Xu*

*Corresponding author for this work

Research output: Contribution to journalJournal articlepeer-review

18 Citations (Scopus)


We employ facile aromatic nucleophilic substitution between the mercapto (-SH) and arylfluoro (Ar-F) groups to achieve extensive and robust cross-linking of a coordination host by porphyrin guests that also serve the purpose of versatile postsynthetic functionalization. For this, a tritopic linker with three trident-like thiol-flanked carboxyl units are reacted with ZrOCl2·8H2O to afford a two-dimensional (3,6-connected) net. The wide aperture of the porous framework solid, together with its stability in both air and boiling water, facilitates the entry of bulky metalloporphyrin guests and the subsequent property studies. On the porphyrin side, four pentafluorophenyl (C6F5-) groups offer multiple fluoro groups to facilitate their replacement by the thiol groups from the host net. The inserted metalloporphyrin bridges impart to the metal-organic framework (MOF) host stable and recyclable activities for photocatalytic hydrogen production. We also disclose an improvement in synthetic methodology, in which BBr3 is used to simultaneously cleave the ester and benzyl thioether groups to more efficiently access thiol-equipped carboxylic acid building block.

Original languageEnglish
Pages (from-to)12643-12649
Number of pages7
JournalInorganic Chemistry
Issue number17
Early online date19 Aug 2020
Publication statusPublished - 8 Sept 2020

Scopus Subject Areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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