Isotope and Hydrogen‐Bond Effects on the Self‐Assembly of Macroions in Dilute Solution

Li, Hui; Shen, Yidan; Yang, Peng; Szymanowski, Jennifer E. S.; Chen, Jiahui; Gao, Yunyi; Burns, Peter C.; Kortz, Ulrich; Liu, Tianbo

doi:10.1002/chem.201902444

Cited by 8 publications

(13 citation statements)

References 65 publications

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“…(8) POMs are valuable models for studying structure-size-property relations such as aggregation behavior in solution because they are larger than most inorganic complexes but smaller than colloids and are dissolvable as macroanions in various solvents. (9) Geochemically important POMs have been preserved in 42 POM minerals (10,11) and are likely important in metal transport in various geochemical and environmental systems. (12) Despite the wide-ranging aforementioned significance of POMs extending from basic scientific interest to sustainable energy applications, little is known about their thermodynamics and stabilities in various systems.…”

Section: Introductionmentioning

confidence: 99%

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

et al. 2020

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Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li-U24, Li-U28, K-U28, Li/K-U60, Mo132, and Mo154, in terms of three components: enthalpy of dissolution (ΔHdiss), enthalpy of formation of aqueous POMs (ΔHf,(aq)), and enthalpy of formation of POM crystals (ΔHf,(c)). ΔHdiss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔHf,(aq) and are more stable than those containing only peroxide bridges. In general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔHf,(aq) can be accurately estimated using only ΔHf,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.

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Section: Introductionmentioning

confidence: 99%

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

et al. 2020

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“…For all samples, the sizes of the blackberry structures (shown by CONTIN analysis) and the rate and activation energy of the assembly (calculated from the change of I 90 over time, Table S1) show no significant difference, except for the slightly faster assembly rate in urea. As urea is a strong hydrogen-bond disruptor, , which would interfere with the intermolecular hydrogen bonds, this slight rate increment indicates that the hydrogen bonds contributed slightly to the inter-{Mo 72 Fe 30 } attraction. , For weaker hydrogen-bond acceptors, e.g., oxoacid (NO 3 – , ClO 4 – , SO 4 2– ) anions, the blackberry formation rate has no significant difference. Therefore, the hydrogen bond is not the major driving force contributing to co-ion effects for small co-ions on the self-assembly of {Mo 72 Fe 30 }.…”

Section: Resultsmentioning

confidence: 94%

“…The influence of co-ions on {SrPd 12 } does not follow the trend in the Hofmeister series. The divergence among different co-ions may come from their roles on affecting the intermolecular hydrogen bonds and hydrophobic interaction. Previous study showed that the rate-determining step for the self-assembly is oligomer formation at the early stage. , The co-ions may compete with {SrPd 12 } at this stage via intermolecular interaction (for oxoacid ions, most likely a hydrogen bond) and slow down the oligomer formation, leading to lower assembly rate.…”

Section: Resultsmentioning

confidence: 99%

“…As urea is a strong hydrogen-bond disruptor, 51,52 which would interfere with the intermolecular hydrogen bonds, this slight rate increment indicates that the hydrogen bonds contributed slightly to the inter-{Mo 72 Fe 30 } attraction. 1,49 For weaker hydrogen-bond acceptors, e.g., oxoacid (NO 3 − , ClO 4 − , SO 4 2− ) anions, 53 the blackberry formation rate has no significant difference. Therefore, the hydrogen bond is not the major driving force contributing to co-ion effects for small co-ions on the self-assembly of {Mo 72 Fe 30 }.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The influence of coions on {SrPd 12 } does not follow the trend in the Hofmeister series. The divergence among different co-ions may come from their roles on affecting the intermolecular hydrogen bonds 49 and hydrophobic interaction. Previous study showed that the rate-determining step for the self-assembly is oligomer formation at the early stage.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Co-ion Effects in the Self-Assembly of Macroions: From Co-ions to Co-macroions and to the Unique Feature of Self-Recognition

et al. 2020

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Macroions, as soluble ions with a size on the nanometer scale, show unique solution behavior different from those of simple ions and large colloidal suspensions. In macroionic solutions, the counterions are known to be important and well-explored. However, the role of co-ions (ions carrying the same type of charge as the macroions) is often ignored. Here, through experimental and simulation studies, we demonstrate the role of co-ions as a function of co-ion size on their interaction with the macroions (using {Mo72Fe30} and {SrPd12} as models) and the related self-assembly into blackberry-type structures in dilute solutions. Several regimes of unique co-ion effects are clearly identified: small ions (halides, oxoacid ions), subnanometer-scaled bulky ions (lacunary Keggin and dodecaborate ions), and those with sizes comparable to the macroions. Small co-ions have no observable effect on the self-assembly of fully hydrophilic {Mo72Fe30}, while due to hydrophobic interaction and intermolecular hydrogen bonds, the small co-ions show influences on the self-assembly of hydrophobic {SrPd12}. Subnanometer ions, a.k.a. “superchaotropic ions”, are still too small to assemble into a blackberry by themselves, but they can coassemble with the macroions, showing a strong interaction with the macroionic system. When the co-ion size is comparable to that of the macroions, they assemble independently instead of assembling with the macroions, leading to the previously reported unique self-recognition phenomenon for macroions.

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Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

et al. 2021

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Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid‐rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry–Perot cavity. Absorption and fluorescence studies indicate a large modification of the self‐assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self‐assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self‐assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.

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Isotope and Hydrogen‐Bond Effects on the Self‐Assembly of Macroions in Dilute Solution

Cited by 8 publications

References 65 publications

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Co-ion Effects in the Self-Assembly of Macroions: From Co-ions to Co-macroions and to the Unique Feature of Self-Recognition

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

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