Transient intermediate in the formation of an amorphous metal-organic framework.

Amorphous metal-organic frameworks are rarely formed via direct synthesis. Our limited understanding of their atomic assembly in solution prevents full exploitation of their unique structural complexity. Here, we use in situ synchrotron X-ray absorption spectroscopy with sub-second time resolution to probe the formation of the amorphous Fe-BTC framework. Using a combination of spectral fingerprinting, linear combination analysis, and principal component analysis coupled with kinetic analyses, we reveal a multi-stage formation mechanism that, crucially, proceeds via the generation of a transient intermediate species.

Formation of a meltable purinate metal-organic framework and its glass analogue.

The chemistries that can be incorporated within melt-quenched zeolitic imidazolate framework (ZIF) glasses are currently limited. Here we describe the preparation of a previously unknown purine-containing ZIF which we name ZIF-UC-7. We find that it melts and forms a glass at one of the lowest temperatures reported for 3D hybrid frameworks.

Formation of new crystalline qtz-[Zn(mIm)2] polymorph from amorphous ZIF-8.

The structure of a new ZIF-8 polymorph with quartz topology (qtz) is reported. This qtz-[Zn(mIm)2] phase was obtained by mechanically amorphising crystalline ZIF-8, before heating the resultant amorphous phase to between 282 and 316 °C. The high-temperature phase structure was obtained from powder X-ray diffraction, and its thermal behaviour, CO2 gas sorption properties and dye adsorption ability were investigated.

Investigating the chemical sensitivity of melting in zeolitic imidazolate frameworks.

The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im)2] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with Tm = 576 °C and Tg = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im)1.35(mIm)0.65], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im)1.995(abIm)0.005] with a lower melting temperature (Tm = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.

Post-Synthetic Modification of a Metal-Organic Framework Glass.

Melt-quenched metal-organic framework (MOF) glasses have gained significant interest as the first new category of glass reported in 50 years. In this work, an amine-functionalized zeolitic imidazolate framework (ZIF), denoted ZIF-UC-6, was prepared and demonstrated to undergo both melting and glass formation. The presence of an amine group resulted in a lower melting temperature compared to other ZIFs, while also allowing material properties to be tuned by post-synthetic modification (PSM). As a prototypical example, the ZIF glass surface was functionalized with octyl isocyanate, changing its behavior from hydrophilic to hydrophobic. PSM therefore provides a promising strategy for tuning the surface properties of MOF glasses.

Principles of melting in hybrid organic-inorganic perovskite and polymorphic ABX3 structures.

Four novel dicyanamide-containing hybrid organic-inorganic ABX3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)2)3] (A = (C3H7)4N, (C4H9)4N, (C5H11)4N; B = Co, Fe, Mn) is analyzed. Structure-property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C3H7)4N → (C4H9)4N → (C5H11)4N was observed to result in a decrease in T m through an increase in ΔS f. Consistent trends in T m with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism.

Mechanochemically synthesised dicyanamide hybrid organic-inorganic perovskites, and their melt-quenched glasses.

Here we present efficient and scalable mechanochemical formation of hybrid organic-inorganic perovskites of the form [TPrA][M(dca)3] (M = Mn2+, Co2+) and the subsequent formation of their bulk melt-quenched glasses. In situ X-ray diffraction reveals direct, facile, and almost instantaneouos formation of both crystalline materials, while slow cooling limits recrystallisation in glasses. The glasses show good stability to acidic and basic aqueous solutions and display higher carbon dioxide uptakes than their crystalline precursors.

Properties of Single-Component Metal-Organic Framework Crystal-Glass Composites.

The formation, and subsequent structural, thermal and adsorptive properties of single-component metal-organic framework crystal-glass composites (MOF-CGCs) are investigated. A series of novel materials exhibiting chemically identical glassy and crystalline phases within the same material were produced, where crystalline ZIF-62(Zn) was incorporated within an ag ZIF-62(Zn) matrix. X-ray diffraction showed that the crystalline phase was still present after heating to above the glass transition temperature of ag ZIF-62(Zn), and interfacial compatibility between the crystalline and glassy phases was investigated using a mixed-metal (ZIF-62(Co))0.5 (ag ZIF-62(Zn))0.5 analogue. CO2 gas adsorption measurements showed that the CO2 uptakes of the MOF-CGCs were between those of the crystalline and glassy phases.

Glassy behaviour of mechanically amorphised ZIF-62 isomorphs.

Zeolitic imidazolate frameworks (ZIFs) can be melt-quenched to form glasses. Here, we present an alternative route to glassy ZIFs via mechanically induced amorphisation. This approach allows various glassy ZIFs to be produced in under 30 minutes at room temperature, without the need for melt-quenching.

Melting of hybrid organic-inorganic perovskites.

Several organic-inorganic hybrid materials from the metal-organic framework (MOF) family have been shown to form stable liquids at high temperatures. Quenching then results in the formation of melt-quenched MOF glasses that retain the three-dimensional coordination bonding of the crystalline phase. These hybrid glasses have intriguing properties and could find practical applications, yet the melt-quench phenomenon has so far remained limited to a few MOF structures. Here we turn to hybrid organic-inorganic perovskites-which occupy a prominent position within materials chemistry owing to their functional properties such as ion transport, photoconductivity, ferroelectricity and multiferroicity-and show that a series of dicyanamide-based hybrid organic-inorganic perovskites undergo melting. Our combined experimental-computational approach demonstrates that, on quenching, they form glasses that largely retain their solid-state inorganic-organic connectivity. The resulting materials show very low thermal conductivities (~0.2 W m-1 K-1), moderate electrical conductivities (10-3-10-5 S m-1) and polymer-like thermomechanical properties.

Identifying the liquid and glassy states of coordination polymers and metal-organic frameworks.

The field of metal-organic frameworks (MOFs) is still heavily focused upon crystalline materials. However, solid-liquid transitions in both MOFs and their parent coordination polymer family are now receiving increasing attention due to the largely unknown properties of both the liquid phase and the glasses that may be formed upon melt-quenching. Here, we argue that the commonly reported concept of 'thermal stability' in the hybrid materials field is insufficient. We present several case studies of the use of differential scanning calorimetry alongside thermogravimetric analysis to prove, or disprove, the cooperative phenomena of melting in several MOF families.

Metal-organic framework and inorganic glass composites.

Metal-organic framework (MOF) glasses have become a subject of interest as a distinct category of melt quenched glass, and have potential applications in areas such as ion transport and sensing. In this paper we show how MOF glasses can be combined with inorganic glasses in order to fabricate a new family of materials composed of both MOF and inorganic glass domains. We use an array of experimental techniques to propose the bonding between inorganic and MOF domains, and show that the composites produced are more mechanically pliant than the inorganic glass itself.

Inducing Social Self-Sorting in Organic Cages To Tune The Shape of The Internal Cavity.

Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host-guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low-symmetry imine cages. Whether a low-energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high-symmetry cages-and the same aldehyde generates low-symmetry socially self-sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low-symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self-sorting.

Production of monodisperse polyurea microcapsules using microfluidics.

Methods to make microcapsules - used in a broad range of healthcare and energy applications - currently suffer from poor size control, limiting the establishment of size/property relationships. Here, we use microfluidics to produce monodisperse polyurea microcapsules (PUMC) with a limonene core. Using varied flow rates and a commercial glass chip, we produce capsules with mean diameters of 27, 30, 32, 34, and 35 µm, achieving narrow capsule size distributions of ±2 µm for each size. We describe an automated method of sizing droplets as they are produced using video recording and custom Python code. The sustainable generation of such size-controlled PUMCs, potential replacements for commercial encapsulated systems, will allow new insights into the effect of particle size on performance.