Designing Glass and Crystalline Phases of Metal–Bis(acetamide) Networks to Promote High Optical Contrast

Liu, Mengtan; Slavney, Adam H.; Tao, Songsheng; McGillicuddy, Ryan D.; Lee, Cassia C.; Wenny, Malia B.; Billinge, Simon J. L.; Mason, Jarad A.

doi:10.1021/jacs.2c10449

Cited by 15 publications

(15 citation statements)

References 69 publications

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“…Notably, this recrystallization is significantly suppressed upon adding even small amounts of water (see Figure S10, Supporting Information). As such, water addition may be used to increase the glass forming ability, which in some HCNGs has been observed to be low, [ 22 ] or tune the properties of mixed glass‐crystal phases. In summary, these observations clearly confirm the universality of the water effect on the melting within the present hmba‐based glass family.…”

Section: Resultsmentioning

confidence: 99%

“…[15] The modifier addition in oxide glasses thus enables a significant chemical diversity that has led to a broad range of applications, from window glasses and touchscreen displays to nuclear waste immobilization, bioactive glasses, and pharmaceutical vials. [20] While some works have been devoted to co-melting and property tuning of MOFs and other coordination networks, e.g., through partial crystallization of glass and ionic liquid facilitated melting, [18,21,22] the lack of a universal method for modification of hybrid glasses is one of the main bottlenecks for exploiting the vivid potentials of this glass family.…”

Section: Introductionmentioning

confidence: 99%

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Water as a Modifier in a Hybrid Coordination Network Glass

Sørensen

Ren

et al. 2023

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The majority of the discovered structures are crystalline and typically synthesized by hydrothermal processes, [5] but recently it has been discovered that some members of this chemical family can form a stable liquid phase upon heating (prior to thermal decomposition), allowing subsequent supercooling into a glassy state. [6][7][8][9] This work has opened a new glass family, [10] notably distinct from the existing metallic, organic, and inorganic glasses, and with possible applications in, e.g., nuclear waste immobilization, [11] thermoelectrics, [4] gas separation, [12] and energy storage, [13] as well as the possibility to produce bulk-sized hybrid organic-inorganic samples (>1 cm 3 ) without grain boundaries. [14] Although these hybrid glasses are chemically distinct from the traditional glass families, they share a number of structural similarities to chemically ordered network glasses (e.g., oxides), as the metallic nodes (for oxides typically Si, Ge, P; for hybrids typically transition metals) bridge through single oxygens and large organic linkers for oxide and hybrid glasses, respectively. [15] Similarly, the metal nodes in the two glass families share the same range of coordination numbers (typically 4-6). [15][16][17] However, there is a major difference in the discovery Chemical diversification of hybrid organic-inorganic glasses remains limited, especially compared to traditional oxide glasses, for which property tuning is possible through addition of weakly bonded modifier cations. In this work, it is shown that water can depolymerize polyhedra with labile metal-ligand bonds in a cobalt-based coordination network, yielding a series of nonstoichiometric glasses. Calorimetric, spectroscopic, and simulation studies demonstrate that the added water molecules promote the breakage of network bonds and coordination number changes, leading to lower melting and glass transition temperatures. These structural changes modify the physical and chemical properties of the melt-quenched glass, with strong parallels to the "modifier" concept in oxides. It is shown that this approach also applies to other transition metal-based coordination networks, and it will thus enable diversification of hybrid glass chemistry, including nonstoichiometric glass compositions, tuning of properties, and a significant rise in the number of glass-forming hybrid systems by allowing them to melt before thermal decomposition.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Water as a Modifier in a Hybrid Coordination Network Glass

Sørensen

Ren

et al. 2023

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“…An empty, hermetically sealed Al pan was used as a reference. Melting temperatures ( T m ) and glass transition temperatures ( T g ) are reported as the extrapolated onset as described in a previous publication …”

Section: Methodsmentioning

confidence: 99%

“…Melting temperatures (T m ) and glass transition temperatures (T g ) are reported as the extrapolated onset as described in a previous publication. 20 Viscosity Measurements. An electromagnetically spinning viscometer (EMS-1000S, Kyoto Electronics Manufacturing Co LTD) was used to measure variable-temperature viscosities.…”

Section: ■ Introductionmentioning

confidence: 99%

Generalizable Synthesis of Highly Fluorinated Ionic Liquids

et al. 2023

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The unique chemistry of fluorocarbons (in particular, their weak intermolecular interactions and high degree of intrinsic free volume) makes them promising building blocks for ionic liquids with high gas capacities. Here, we report a generalizable method for the synthesis of fluorinated ionic liquids, which relies on the evolution of gaseous byproducts to drive product formation. This synthetic strategy overcomes solubility challenges that can hinder the synthesis of highly fluorinated ionic liquids via conventional methods and enables a systematic investigation of the effect of fluorination on ionic liquid viscosity and gas solubility.

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“…5–8 They show promising functions including selective gas permeability, ion transport, protection, and optical switching. 9–16…”

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confidence: 99%