Conjugated porous polymers (CPPs), a class of fully crosslinked polymers, as heterogeneous photocatalysts are reviewed revealing a wide range of chemical transformations including hydrogen production, organic synthesis and photopolymerization.

Self-standing thiol (-SH) groups within a Zr(IV)-based metal-organic framework (MOF) anchor Pd(II) atoms for catalytic applications: the spatial constraint prevents the thiol groups from sealing off/poisoning the Pd(II) center, while the strong Pd-S bond precludes Pd leaching, enabling multiple cycles of heterogeneous catalysis to be executed.

We report the dramatic triggering of structural order in a Zr(IV)-based metal−organic framework (MOF) through docking of HgCl 2 guests. Although as-made crystals were unsuitable for single crystal X-ray diffraction (SCXRD), with diffraction limited to low angles well below atomic resolution due to intrinsic structural disorder, permeation of HgCl 2 not only leaves the crystals intact but also resulted in fully resolved backbone as well as thioether side groups. The crystal structure revealed elaborate HgCl 2 -thioether aggregates nested within the host octahedra to form a hierarchical, multifunctional net. The chelating thioether groups also promote Hg(II) removal from water, while the trapped Hg(II) can be easily extricated by 2-mercaptoethanol to reactivate the MOF sorbent.

Hard-and-soft combo does the trick: hard and robust Zr(iv)-carboxylate nodes build up the net, while soft allyl and sulfur donors selectively extract Pd(ii)-from amongst other elements in nuclear wastes.

An efficient, wide-scope synthesis of thiol-equipped MOF solids offers ever stronger binding for mercury pollutants and broader horizons for functionalization of porous materials.

Molecular components of opposite character are often incorporated within a single system, with a rigid core and flexible side arms being a common design choice. Herein, molecule L has been designed and prepared featuring the reverse design, with rigid side arms (arylalkynyl) serving to calibrate the mobility of the flexible polyether links in the core. Crystallization of this molecule with Pb(II)  ions led to a dynamic metal-organic framework (MOF) system that not only exhibits dramatic, reversible single-crystal-to-single-crystal transformations, but combines distinct donor and acceptor characteristics, allowing for substantial uptake of PdCl2 and colorimetric sensing of H2 S in water.

Thiol groups (−SH) offer versatile reactivity for functionalizing metal–organic frameworks, and yet thiol-equipped MOF solids remain underexplored due to synthetic challenges. Building on the recent breakthrough using benzyl mercaptan as the sulfur source and AlCl3 for uncovering the thiol function, we report on the thiol-equipped linker 3,3′-dimercaptobiphenyl-4,4′-dicarboxylic acid and its reaction with Zr­(IV) ions to form a UiO-67-type MOF solid with distinct functionalities. The thiol-equipped UiO-67 scaffold shows substantial stability toward oxidation, e.g., it can be treated with 30% H2O2 to afford oxidation of the thiol to the strongly acidic sulfonic function while maintaining the ordered porous MOF structure. The thiol groups also effectively take up palladium­(II) ions from solutions to allow for comparative studies on catalytic activities and to help elucidate how the spatial configuration of the thiol groups can be engineered to impact the performance of heterogeneous catalysis in the solid state. Comparative studies on the stability in the solventless (activated) state also help to highlight the steric factor in stabilizing UiO-67-type frameworks.

Synergism between oxygen and sulfur donors allows highly variable thioether side chains to be built into the matrices of Zr(iv)–carboxylate networks, boosting the functionality and stability of this promising class of porous solids.