Self-assembly in soft matter with multiple length scales

Spontaneous self-assembly in molecular systems is a fundamental route to both biological and engineered soft matter. Simple micellization, emulsion formation, and polymer mixing are well understood. However, the principles behind emergence of structures with competing length scales in soft matter systems remain unknown. Examples include droplet-inside-droplet assembly in many biomacromolecular systems undergoing liquid-liquid phase separation, analogous multiple emulsion formation in oil-surfactant-water formulations, and polymer core-shell particles with internal structure. We develop here a microscopic theoretical model based on effective interactions between the constituents of a soft matter system to explain self-organization both at single and multiple length scales. The model identifies how spatial ordering at multiple length scales emerges due to competing interactions between the system components, e.g., molecules of different sizes and different chemical properties. As an example of single and multiple length scale assembly, we map out a generic phase diagram for a solution with two solute species differing in their mutual and solvent interactions. We further connect the phase diagram to a molecular system via molecular simulations of a block-copolymer system that has a transition from regular single-core polymer particles to multicore aggregates that exhibit multiple structural length scales. The findings provide guidelines to understanding the length scales rising spontaneously in biological self-assembly but also open venues to the development and engineering of biomolecular and polymeric functional materials and pharmaceutical formulations

Supplementary information files for: Self-assembly in soft matter with multiple length scales

Supplementary files for article: Self-assembly in soft matter with multiple length scales.Spontaneous self-assembly in molecular systems is a fundamental route to both biological and engineered soft matter. Simple micellization, emulsion formation, and polymer mixing are well understood. However, the principles behind emergence of structures with competing length scales in soft matter systems remain unknown. Examples include droplet-inside-droplet assembly in many biomacromolecular systems undergoing liquid-liquid phase separation, analogous multiple emulsion formation in oil-surfactant-water formulations, and polymer core-shell particles with internal structure. We develop here a microscopic theoretical model based on effective interactions between the constituents of a soft matter system to explain self-organization both at single and multiple length scales. The model identifies how spatial ordering at multiple length scales emerges due to competing interactions between the system components, e.g., molecules of different sizes and different chemical properties. As an example of single and multiple length scale assembly, we map out a generic phase diagram for a solution with two solute species differing in their mutual and solvent interactions. We further connect the phase diagram to a molecular system via molecular simulations of a block-copolymer system that has a transition from regular single-core polymer particles to multicore aggregates that exhibit multiple structural length scales. The findings provide guidelines to understanding the length scales rising spontaneously in biological self-assembly but also open venues to the development and engineering of biomolecular and polymeric functional materials and pharmaceutical formulations.</div

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity

Hybrid ultramicroporous materials (HUMs), metal–organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62– pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g–1) which is paired with low uptake of CO2 (–1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol–1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry