NU-1000 is a robust, mesoporous metal-organic framework (MOF) with hexazirconium nodes ([ZrOH], referred to as oxo-Zr nodes) that can be synthesized by combining a solution of ZrOCl·8HO and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as HTBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo-Zr nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo-Zr node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurally heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.

We report measurements of adsorption isotherms and the determination of the isosteric heats of adsorption of several small gases (H, D, Ne, N, CO, CH, CH, Ar, Kr, and Xe) on the metal-organic framework (MOF) NU-1000, which is one of the most thermally stable MOFs. It has transition-metal nodes of formula Zr(μ-OH)(μ-O)(OH)(OH) that resemble hydrated ZrO clusters and can serve as catalysts or catalyst supports. The linkers in this MOF are pyrenes linked to the nodes via the carboxylate groups of benzoates. The broad range of adsorbates studied here allows us to compare trends both with adsorption on other surfaces and with density functional calculations also presented here. The experimental isotherms indicate similar filling of the MOF surface by the different gases, starting with strong adsorption sites near the Zr atoms, a result corroborated by the density functional calculations. This adsorption is followed by the filling of other adsorption sites on the nodes and organic framework. Capillary condensation occurs in wide pores after completion of a monolayer. The total amount adsorbed for all the gases is the equivalent of two complete monolayers. The experimental isosteric heats of adsorption are nearly proportional to the atom-atom (or molecule-molecule) Lennard-Jones well-depth parameters of the adsorbates but ∼13-fold larger. The density functional calculations show a similar trend but with much more scatter and heats that are usually greater (by 30%, on average).

Spin–spin interactions between two identical aromatic radicals have been studied extensively and utilized to establish supramolecular recognition. Here we report that spin-pairing interactions could also take place between two different π-electron radicals, namely a bipyridinium radical cation (BPY+•) and a naphthalene-1,8:4,5-bis(dicarboximide) radical anion (NDI─•). The occurrence of this type of previously unreported hetero radical-pairing interactions is attributed to enhancement effect of Coulombic attraction between these two radicals bearing opposite charges. The Coulombic-enhanced hetero radical pairing interactions are employed to drive host–guest recognition, as well as the reversible switching of a bistable [2]rotaxane.