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 ZrOCl 2 •8H 2 O 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 (C 6 F 5 −) 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 BBr 3 is used to simultaneously cleave the ester and benzyl thioether groups to more efficiently access thiol-equipped carboxylic acid building block.

Donor-acceptor two-dimensional covalent organic frameworks PD- COF-23 and PD-COF-23-Ni are constructed, and applied for selective CO2 redution with 20.9 µmol g−1 h−1 and 40.0 µmol g−1 h−1 CO conversion, respectively,...

Covalent triazine frameworks (CTFs) with two-dimensional conjugated structures and a high nitrogen content have potential for photocatalytic hydrogen evolution (PHE). Herein, we show a strategy to boost the photocatalytic performance of a CTF containing bipyridine (bpy) units (PhBp-CTF). Through a postcomplexation reaction of the PhBp-CTF with Ir2(ppy)4(μ-Cl)2, the Ir complexes of [Ir­(bpy)­(ppy)2]3+ are successfully embedded inside to form PhBp-CTF-Ir. The accurate content and valence state of Ir have been confirmed by advanced spectroscopies. PhBp-CTF-Ir shows a PHE rate of 4805 μmol g–1 h–1, while its precursor without Ir complexes has a rate of 3175 μmol g–1 h–1. The enhanced photocatalytic performance is attributed to the Ir complexes inside PhBp-CTF-Ir, which act as not only an effective photosensitizer but also a proton reduction catalyst.