A linker molecule with four pendant thiophene functions was crystallized with Zr(IV) ions to form a semiconductive porous coordination solid (1.1 × 10-5 S cm-1). Oxidative treatment by FeCl3 guests...

The series of highly stable porous solids here feature systematic, regiospecific sulfur substitutions on the organic linkers for versatile functions. One major surprise lies in the controllable sequential reactions between sodium thiomethoxide (NaSMe) and octafluorobiphenyl-4,4′-dicarboxylic acid (H 2 bpdc-8F; this was readily made without precious metal catalysts). Namely, 3, 4, 6, and 8 methylthio-substitutions can be respectively achieved with regiospecificity (i.e., to produce the four molecules H 2 bpdc-3S5F, H 2 bpdc-4S4F, H 2 bpdc-6S2F, H 2 bpdc-8MS). A second surprise lies in their persistent formation of the UiO-67type net with Zr(IV) ions, e.g., even in the case of the fully sulfurated H 2 bpdc-8MS. In addition to the remarkable breadth of functional control, all the Zr(IV)-based crystalline solids here are stable in boiling water (e.g., for 24 h) and in air as solventless, activated porous solids. Moreover, the thioether groups allow for convenient H 2 O 2 oxidation to fine-tune the hydrophilicity and luminescence properties and improve proton conductivity.Article pubs.acs.org/IC

F 2 (SO 3 H) 2 manifests a superprotonic conductivity of 2.86 S cm −1 (at 90% RH and 90 °C), a record breaker so far. Supported by joint experimental−theoretical studies, the ultrahigh conductivity originates from conduction by protons rather than ions and is rationalized to result from the enhanced acidity of −SO 3 H by introduction of electronegative −F followed by the formation of double charged layers composed of Li + and −SO 3 − layers after encapsulation of LiCl. Importantly, the effect of charged layers has been verified, and charged-layer-mediated proton conduction is unprecedentedly proposed to fill in the missing pieces in existing proton conduction mechanisms, giving insight into the rational design of superprotonic conducting framework materials potentially applied as proton exchange membranes in fuel cells.

A tripodal linker with six pendant methylthio (-SCH3) groups was crystallized with Zn(II) ions to provide metal-organic framework (MOF) crystals, namely NOTT-6SMe-Zn, bearing three kinds of cage-like pores. NOTT-6SMe-Zn gives...

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