Metal Effects on the Sensitivity of Isostructural Metal-Organic Frameworks Based on 5-Amino-3-nitro-1H-1,2,4-triazole.

Two energetic metal-organic frameworks (MOFs), Co-ANTA and Zn-ANTA, are synthesized from 5-amino-3-nitro-1H-1,2,4-triazole (ANTA) and exhibit superior oxygen balance, density, and thermal stability compared to ANTA. The superior oxygen balance is achieved through a combination of hydroxide ligands and deprotonated linkers. Although the materials are isostructural and have similar density, oxygen balance, and sensitivity to heat, their impact sensitivities are significantly different. Similar to ANTA, Zn-ANTA is fairly insensitive to impact. By contrast, the impact sensitivity of ANTA is increased significantly after coordination polymerization with cobalt. The disparate impact sensitivities of the compounds might be attributed to the different electronic configurations of the metal ions constituting the frameworks.

Thermal decomposition pathways of nitro-functionalized metal-organic frameworks.

The decomposition behavior of high energy metal-organic frameworks (MOFs) with extensive nitration is disclosed. In contrast to the detonation behavior observed in molecular energetic compounds, deflagration transforms cubic MOFs into anisotropic carbon structures with highly dispersed metal. Both the structural metal and intimate mixing are found to be critical.

MOF-5-Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption.

An unprecedented mode of reactivity of Zn4 O-based metal-organic frameworks (MOFs) offers a straightforward and powerful approach to polymer-hybridized porous solids. The concept is illustrated with the production of MOF-5-polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF-5 crystals after heating in pure styrene for 4-24 h. The surface area and polystyrene content of the material can be fine-tuned by controlling the duration of heating styrene in the presence of MOF-5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF-5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF-5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.

Rendering non-energetic microporous coordination polymers explosive.

Adsorption of oxidizing guest molecules into a non-energetic microporous coordination polymer produces explosives with desirable oxygen balance, high heat released upon decomposition, and suppressed vapor pressure of the guest. Here, this results in primary explosives, materials very sensitive to impact, that have the potential to be used as replacements for lead-based initiators.

Polymer@MOF@MOF: "grafting from" atom transfer radical polymerization for the synthesis of hybrid porous solids.

The application of a core-shell architecture allows the formation of a polymer-coated metal-organic framework (MOF) maintaining high surface area (2289-2857 m(2) g(-1)). The growth of a MOF shell from a MOF core was used to spatially localize initiators by post-synthetic modification. The confinement of initiators ensures that polymerization is restricted to the outer shell of the MOF.