Increasing the stability of calixarene-capped porous cages through coordination sphere tuning.

Chemically and thermally stable permanently porous coordination cages are appealing candidates for separations, catalysis, and as the porous component of new porous liquids. However, many of these applications have not turned to microporous cages as a result of their poor solubility and thermal or hydrolytic stability. Here we describe the design and modular synthesis of iron and cobalt cages where the carboxylate groups of the bridging ligands of well-known calixarene capped coordination cages have been replaced with more basic triazole units. The resultingly higher M-L bond strengths afford highly stable cages that are amenable to modular synthetic approaches and potential functionalization or modification. Owing to the robust nature of these cages, they are highly processable and are isolable in various physical states with tunable porosity depending on the solvation methods used. As the structural integrity of the cages is maintained upon high activation temperatures, apparent losses in porosity can be mediated by resolvation and crystallization or precipitation.

Rapid post-synthetic modification of porous coordination cages with copper-catalyzed click chemistry.

Novel cobalt calixarene-capped and zirconium-based porous coordination cages were prepared with alkyne and azide functionality to leverage post-synthetic modification by click chemistry. While the calixarene-capped cages showed impressive stability when exposed to the most straightforward copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction conditions with copper(II) sulfate and sodium ascorbate as the reducing agent, milder reaction conditions were necessary to perform analogous CuAAC reactions on zirconium-based cages. Reaction kinetics were monitored by IR spectroscopy, confirming rapid reaction times (<3 hours).

Porous Salts as Platforms for Heterogeneous Catalysis.

The preparation of a new class of reactive porous solids, prepared via straightforward salt metathesis reactions, is described here. Reaction of the dimethylammonium salt of a magnesium-based porous coordination cage with the chloride salt of [CrII Cl(Me4 cyclam)]+ affords a porous solid with concomitant removal of dimethylammonium chloride. The salt consists of the ions combined in the expected ratio based on their charge as confirmed by UV-vis and X-ray photoelectron spectroscopies, ion chromatography (IC), and inductively coupled plasma mass spectrometry (ICP-MS). The porous salt boasts a Brunauer-Emmett-Teller (BET) surface area of 213 m2  g-1 . Single crystal X-ray diffraction reveals the chromium(II) cations in the structure reside in the interstitial space between porous cages. Importantly, the chromium(II) centers, previously shown to react with O2 to afford reactive chromium(III)-superoxide adducts, are still accessible in the solid state as confirmed by UV-vis spectroscopy. The site-isolated reactive centers have competence toward hydrogen atom abstraction chemistry and display significantly increased stability and reactivity as compared to dissolved ions.

Multi-technique structural analysis of zinc carboxylates (soaps).

A series of medium- and long-chain zinc carboxylates (zinc octanoate, zinc nonanoate, zinc decanoate, zinc undecanoate, zinc dodecanoate, zinc pivalate, zinc stearate, zinc palmitate, zinc oleate, and zinc azelate) was analyzed by ultra-high-field 67Zn NMR spectroscopy up to 35.2 T, as well as 13C NMR and FTIR spectroscopy. We also report the single-crystal X-ray diffraction structures of zinc nonanoate, zinc decanoate, and zinc oleate-the first long-chain carboxylate single-crystals to be reported for zinc. The NMR and X-ray diffraction data suggest that the carboxylates exist in three distinct geometric groups, based on structural and spectroscopic parameters. The ssNMR results presented here present a future for dynamic nuclear polarization (DNP)-NMR-based minimally invasive methods for testing artwork for the presence of zinc carboxylates.

Aluminum-based metal-organic framework nanoparticles as pulmonary vaccine adjuvants.

The adoption of pulmonary vaccines to advantageously provide superior local mucosal protection against aerosolized pathogens has been faced with numerous logistical and practical challenges. One of these persistent challenges is the lack of effective vaccine adjuvants that could be well tolerated through the inhaled route of administration. Despite its widespread use as a vaccine adjuvant, aluminum salts (alum) are not well tolerated in the lung. To address this issue, we evaluated the use of porous aluminum (Al)-based metal-organic framework (MOF) nanoparticles (NPs) as inhalable adjuvants. We evaluate a suite of Al-based MOF NPs alongside alum including DUT-4, DUT-5, MIL-53 (Al), and MIL-101-NH2 (Al). As synthesized, MOF NPs ranged between ~ 200 nm and 1 µm in diameter, with the larger diameter MOFs matching those of commercial alum. In vitro examination of co-stimulatory markers revealed that the Al-based MOF NPs activated antigen presenting cells more effectively than alum. Similar results were found during in vivo immunizations utilizing ovalbumin (OVA) as a model antigen, resulting in robust mucosal humoral responses for all Al MOFs tested. In particular, DUT-5 was able to elicit mucosal OVA-specific IgA antibodies that were significantly higher than the other MOFs or alum dosed at the same NP mass. DUT-5 also was uniquely able to generate detectable IgG2a titers, indicative of a cellular immune response and also had superior performance relative to alum at equivalent Al dosed in a reduced dosage vaccination study. All MOF NPs tested were generally well-tolerated in the lung, with only acute levels of cellular infiltrates detected and no Al accumulation; Al content was largely cleared from the lung and other organs at 28 days despite the two-dose regime. Furthermore, all MOF NPs exhibited mass median aerodynamic diameters (MMADs) of ~ 1.5-2.5 µm when dispersed from a generic dry powder inhaler, ideal for efficient lung deposition. While further work is needed, these results demonstrate the great potential for use of Al-based MOFs for pulmonary vaccination as novel inhalable adjuvants.

Anion Binding as a Strategy for the Synthesis of Porous Salts.

Porous salts have recently emerged as a promising new class of ultratunable permanently microporous solids. These adsorbents, which were first reported as ionic solids based on porous cations and anions, can be isolated from a wide variety of charged, permanently porous coordination cages. A challenge in realizing the full tunability of such systems, however, lies in the fact that the majority of coordination cages for which surface areas have been reported are comprised of charge-balanced inorganic and organic building blocks that result in neutral cages. As such, most reported permanently porous coordination cages cannot be used as reagents in the synthesis of porous salts. Here, we show that the facile reaction of TBAX (TBA+ = tetra-n-butylammonium; X = F- and Cl-) with molybdenum paddlewheel-based coordination cages of the M4L4 and M24L24 lantern and cuboctahedra structure types, respectively, affords charged cages by virtue of coordination of halide anions to the internal and/or external metal sites on these structures, as confirmed by single-crystal X-ray diffraction, X-ray photoelectron spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. At a practical level, the TBAX/cage reactions, which are fully reversible upon isolation of the cage with the appropriate solvent, solubilize otherwise rigorously insoluble cages. This method significantly increases the solution processability of these highly porous solids. Toward the formation of new porous salts, halide binding also serves to incorporate charge on neutral cages and make them amenable to simple salt metathesis reactions to afford new porous salts based on anions and cations with intrinsic porosity. A combination of diffraction methods and a suite of spectroscopic tools confirms speciation of the isolated solids, which represent a new class of highly tunable porous salts. Ultimately, this work represents a roadmap for the preparation of new porous solids and showcases the utility and broad applicability of anion binding as a strategy for the synthesis of porous salts.

Synthesis and Characterization of an Isoreticular Family of Calixarene-Capped Porous Coordination Cages.

Functionalization of permanently porous coordination cages has been used to tune phase, surface area, stability, and solubility in this promising class of adsorbents. For many cages, however, these properties are intricately tied together, and installation of functional groups, for example, to increase solubility often leads to a decrease in surface area. Calixarene-capped cages offer the advantage in that they are cluster-terminated cages whose solid-state packing, and thus surface area, is typically governed by the nature of the capping ligand rather than the bridging ligand. In this work we investigate the influence of ligand functionalization on two series of isoreticular Ni(II)- and Co(II)-based calixarene-capped cages. The two types of materials described are represented as octahedral and rectangular prismatic coordination cages and can be synthesized in a modular manner, allowing for the substitution of dicarboxylate bridging ligands and the introduction of functional groups in specific locations on the cage. We ultimately show that highly soluble cages can be obtained while still having access to high surface areas for many of the isolated phases.

Gas Storage in Porous Molecular Materials.

Molecules with permanent porosity in the solid state have been studied for decades. Porosity in these systems is governed by intrinsic pore space, as in cages or macrocycles, and extrinsic void space, created through loose, intermolecular solid-state packing. The development of permanently porous molecular materials, especially cages with organic or metal-organic composition, has seen increased interest over the past decade, and as such, incredibly high surface areas have been reported for these solids. Despite this, examples of these materials being explored for gas storage applications are relatively limited. This minireview outlines existing molecular systems that have been investigated for gas storage and highlights strategies that have been used to understand adsorption mechanisms in porous molecular materials.

Using Low-Pressure Methane Adsorption Isotherms for Higher-Throughput Screening of Methane Storage Materials.

A useful correlation between the low-pressure (up to 1.2 bar), low-temperature (195 K) and high-pressure (up to 65 bar), room temperature (298 K) methane storage properties of a range of porous materials is reported. Methane isotherms under these two sets of conditions show a remarkable agreement in both equilibrium adsorption and deliverable capacities for materials with pore volumes that are less than approximately 0.80 cm3/g. This trend holds well for the suite of metal-organic frameworks and porous coordination cages we studied, in addition to a zeolite and porous organic cage. Although it is well known that gravimetric gas storage capacity trends with gravimetric surface area, the 1.2 bar, 195 K excess adsorption capacity of a given framework is a better indicator of its room temperature, 65 bar capacity. Given the significantly smaller sample quantities needed for low-pressure measurements, greater accessibility to researchers around the world, accuracy of the measurement, and higher throughput, we envision this method as a rapid screening tool for the identification of methane storage materials. As excess/total adsorption and gravimetric/volumetric adsorption can be interconverted by simple utilization of the scalar quantities of pore volume or density, respectively, this method can be easily adapted to obtain both gravimetric and volumetric total adsorption capacities for a given adsorbent. In terms of volumetric methane adsorption, we further investigate the relationship between crystallographic and bulk density for the adsorbents studied here. With this analysis, it becomes apparent that in the absence of novel synthetic approaches, reported volumetric storage capacities should be viewed as an optimistic upper limit for a given material and not necessarily a true reflection of its actual adsorption properties as most MOFs have bulk densities that are less than half of their crystallographic values.

Synthesis and characterization of low-nuclearity lantern-type porous coordination cages.

Permanent porosity in lantern-type M4L4 paddlewheel-based cages is rare and has only been reported for naphthalene, naphthyridine, and diethynylbenzene-based linkers. This work presents the design, synthesis, and characterization of small lanterns that exhibit CO2 accessible BET surface areas in excess of 200 m2 g-1. The crystal packing and porosity of these cages can be tuned by either ligand functionalization or the choice of M2+ source used in their synthesis. Given their low nuclearity, these cages with internal M-M distances of less than 5 Å represent the lower size limit for permanently microporous coordination cages.