Free-standing, accessible thiol (-SH) functions have been installed in robust, porous coordination networks to provide wide-ranging reactivities and properties in the solid state. The frameworks were assembled by reacting ZrCl4 or AlCl3 with 2,5-dimercapto-1,4-benzenedicarboxylic acid (H2DMBD), which features the hard carboxyl and soft thiol functions. The resultant Zr-DMBD and Al-DMBD frameworks exhibit the UiO-66 and CAU-1 topologies, respectively, with the carboxyl bonded to the hard Zr(IV) or Al(III) center and the thiol groups decorating the pores. The thiol-laced Zr-DMBD crystals lower the Hg(II) concentration in water below 0.01 ppm and effectively take up Hg from the vapor phase. The Zr-DMBD solid also features a nearly white photoluminescence that is distinctly quenched after Hg uptake. The carboxyl/thiol combination thus illustrates the wider applicability of the hard-and-soft strategy for functional frameworks.

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Melt‐processed organic–inorganic perovskite channel layers (see Figure) are demonstrated in field‐effect transistors fabricated on both silicon and polyimide substrates. Linear and saturation regime field‐effect mobilities for the melt‐processed devices are enhanced relative to the values achieved for analogous spin‐coated devices due, at least in part, to the improved grain structure of the melt‐processed films.

Investigations on molecular variants of the 3-fold symmetric 1,3,5-tris(4-ethynylbenzonitrile)benzene crystallized with silver triflate revealed a nearly invariant pseudohexagonal porous structure type. Modifications involved the attachment of pendant groups to the central aromatic ring of the parent molecule. Pendant groups include the vinyl group, stilbene, the chiral group myrtanol, and groups with different chemical functionalities such as alcohols, ethers, and esters. Modifications also included the addition of elongated spacer units between the central benzene ring and the peripheral nitrile groups. In these molecules the acetylene bridges of 1,3,5-tris(4-ethynylbenzonitrile)benzene were replaced with diacetylene, ethynylbenzene, and diethynylbenzene type units. Single-crystal refinements for pentoxy-2,4,6-tris(4-ethynylbenzonitrile)benzene·AgOTf and 1,3,5-tris(4-(4-ethynylbenzonitrile)phenyl)benzene·AgOTf as well as powder data on 12 crystalline phases showed the consistent formation of pseudohexagonal channels, demonstrating that the parent porous architecture is stable both to functional modification of the interior of the channel as well as to enlargement of the pores. Pentoxy-2,4,6-tris(4-ethynylbenzonitrile)benzene·AgOTf refined in the monoclinic space group Am. 1,3,5-Tris(4-(4-ethynylbenzonitrile)phenyl)benzene·AgOTf was found to be triclinic with space group P1̄. These crystals have pseudohexagonal channels respectively 15 and 25 Å in diameter. Cell constants based on powder data are compatible with channel diameters ranging from 10 to 30 Å. The latter channel diameters are among the largest known for organic porous solids. The introduction of the chiral myrtanol unit led to the preparation of a chiral porous solid. The thermal and chemical stabilities of these phases were investigated. The pseudohexagonal structure proved stable to complete solvent loss from the channel. It was found in the case of a host with alcohol functionality that an acid anhydride guest, trifluoroacetic anhydride, reacted with the host to form an ester with retention of the porous structure type.

Healable silicone materials have great technical impact in coatings, smart actuators, and flexible electronics, however, current healable silicone materials lack mechanical tunability. Herein, we designed and synthesized a new type of healable silicone through hydrogen-bond assisted multiphase assembly of siloxane oligomers. Besides the enhanced mechanical strength, unique water-enhanced healing was observed in the polymer network which is due to the reversible dissociation/association of multivalent hydrogen bonds in the presence of water.