A mixed molecular salt of lithium and sodium breaks the Hume-Rothery rules for solid solutions

Lestari, Monica; Lusi, Matteo

doi:10.1039/c8cc09850f

Cited by 15 publications

(12 citation statements)

References 27 publications

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“…More recently, mixing components has been extended from inorganic solids − and molecular crystals − to framework materials. , In contrast to inorganic alloys, the design of framework materials relies on building blocks that form bonds in specific directions to favor the formation of a periodic structure . Useful properties emerge as a consequence of monomer design and framework topology .…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Covalent Organic Framework Solid Solutions

Yang

Flanders

et al. 2021

J. Am. Chem. Soc.

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Covalent organic frameworks (COFs) generally leverage one or two monomers with specific sizes and shapes to access highly symmetric and periodic polymer networks. Almost all reported COFs employ the minimum sets of monomers needed for the polymerization (usually two, sometimes one) and crystallize in high-symmetry topologies. COFs synthesized from more than two monomers usually employ mixtures with different pendant functionalities to distribute these groups statistically throughout the structure, or monomers with different sizes in ratios targeting lower symmetry topologies. Here, we demonstrate that mixtures of monomers with different lengths generate single-phase, hexagonal two-dimensional covalent organic framework (2D COF) solid solutions at continuously variable feed ratios. X-ray diffraction measurements, Fourier-transform infrared spectroscopy, and Pawley refinement indicate that both monomers distribute randomly within the same lattice, and the lattice parameters continuously increase as more of the larger linker is incorporated. Furthermore, COF solid solutions are accessed directly by polymerizing a mixture of monomers but not via linker exchange from a preformed COF. As strain develops from the lattice accommodating monomers with different sizes, the nonlinear relationship between the monomer incorporation and the COF's lattice parameters suggests that bond-bending of the monomers plays a role in incorporating monomers of different lengths into the solid solutions. Solid solution formation represents a new strategy to design 2D COFs and increase their complexity. Specifically, varying the monomer composition of a given network enables many properties, such as the average pore size, to be continuously tuned between those of corresponding pure COFs.

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Section: Introductionmentioning

confidence: 99%

Two-Dimensional Covalent Organic Framework Solid Solutions

Yang

Flanders

et al. 2021

J. Am. Chem. Soc.

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“… 27 Interestingly, both NiFe 2 O 4 and CoFe 2 O 4 are isostructural and consist of isovalent Ni 2+ and Co 2+ , thus they are characterized by the ability to form a highly diverse range of substitutional solid solutions following Hume-Rothery rules. 28 The resultant effect is an enhancement of the overall properties as the mixed nickel–cobalt ferrite solid solution is an electrochemically efficient material compared to the pristine NiFe 2 O 4 and CoFe 2 O 4 .…”

Section: Introductionmentioning

confidence: 99%

Solventless synthesis of nanospinel Ni_1−xCo_xFe₂O₄ (0 ≤ x ≤ 1) solid solutions for efficient electrochemical water splitting and supercapacitance

et al. 2021

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“…In contrast, recent work shows that appropriate design strategies can enable mixed crystals despite the lack of isostructurality (Schur et al, 2015) or large size difference (Lestari & Lusi, 2019) of the parent components. Other works show that the appropriate synthetic conditions could afford long-lasting metastable products -as an example, solventassisted grinding can afford solid solutions that are not available by conventional techniques (Chierotti et al, 2010).…”

Section: Introductionmentioning

confidence: 95%

Cortisone and cortisol break hydrogen-bonding rules to make a drug–prodrug solid solution

Verma¹,

Bordignon²,

Chierotti³

et al. 2020

Int Union Crystallogr J

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Multidrug products enable more effective therapies and simpler administration regimens, provided that a stable formulation is prepared, with the desired composition. In this view, solid solutions have the advantage of combining the stability of a single crystalline phase with the potential of stoichiometry variation of a mixture. Here a drug–prodrug solid solution of cortisone and cortisol (hydrocortisone) is described. Despite the structural differences of the two components, the new phase is obtained both from solution and by supercritical CO2 assisted spray drying. In particular, to enter the solid solution, hydrocortisone must violate Etter's rules for hydrogen bonding. As a result, its dissolution rate is almost doubled.

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A mixed molecular salt of lithium and sodium breaks the Hume-Rothery rules for solid solutions

Abstract: Despite the difference in size and chemistry, lithium and sodium form a solid solution as isoorotate salt. Such behaviour, which represents an exception to the Hume-Rothery rules, can be exploited in the preparation of novel lithium drugs.

Cited by 15 publications

References 27 publications

Two-Dimensional Covalent Organic Framework Solid Solutions

Two-Dimensional Covalent Organic Framework Solid Solutions

Solventless synthesis of nanospinel Ni_1−xCo_xFe₂O₄ (0 ≤ x ≤ 1) solid solutions for efficient electrochemical water splitting and supercapacitance

Cortisone and cortisol break hydrogen-bonding rules to make a drug–prodrug solid solution

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A mixed molecular salt of lithium and sodium breaks the Hume-Rothery rules for solid solutions

Abstract: Despite the difference in size and chemistry, lithium and sodium form a solid solution as isoorotate salt. Such behaviour, which represents an exception to the Hume-Rothery rules, can be exploited in the preparation of novel lithium drugs.

Cited by 15 publications

References 27 publications

Two-Dimensional Covalent Organic Framework Solid Solutions

Two-Dimensional Covalent Organic Framework Solid Solutions

Solventless synthesis of nanospinel Ni1−xCoxFe2O4 (0 ≤ x ≤ 1) solid solutions for efficient electrochemical water splitting and supercapacitance

Cortisone and cortisol break hydrogen-bonding rules to make a drug–prodrug solid solution

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Product

Resources

About

Solventless synthesis of nanospinel Ni_1−xCo_xFe₂O₄ (0 ≤ x ≤ 1) solid solutions for efficient electrochemical water splitting and supercapacitance