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Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids
Stockholm University, Sweden; Aarhus University, Denmark.
Stockholm University, Sweden; Aarhus University, Denmark.
KTH Royal Institute of Technology, Sweden.
KTH Royal Institute of Technology, Sweden.
Vise andre og tillknytning
2023 (engelsk)Inngår i: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 29, artikkel-id 2300912Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]−, bis(mandelato)borate, [BMB]− and bis(salicylato)borate, [BScB]−, are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]− by [BMB]−, or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems. © 2023 The Authors.

sted, utgiver, år, opplag, sider
John Wiley and Sons Inc , 2023. Vol. 29, artikkel-id 2300912
Emneord [en]
ionic liquids, nanostructures, orthoborates, small angle neutron scattering, Alkylation, Negative ions, Network architecture, Neutron scattering, Positive ions, Alkyl chain lengths, Bicontinuous, Imidazolium, Imidazolium cation, Molecular architecture, Nanostructured systems, Ortho-borates, Oxalato, Phosphonium cations, Small-angle neutron scattering
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Identifikatorer
URN: urn:nbn:se:ri:diva-65716DOI: 10.1002/smll.202300912Scopus ID: 2-s2.0-85163735321OAI: oai:DiVA.org:ri-65716DiVA, id: diva2:1786461
Merknad

The authors thank STFC ISIS Neutron & Muon Source forSwedish Foundation for Strategic Research (“REFIT” project EM16-0013),the Knut and Alice Wallenberg Foundation (project KAW2012.0078), theSwedish Research Council (projects 2018–05017 and 2017–04080) aregratefully acknowledged. AVM acknowledges the Royal Swedish Academyof Sciences for support through the Göran Gustafsson prize in Chemistryand the Villum Foundation for a Villum Investigator award. Dr Liliana deCampo is thanked for useful discussions. The ToC graphic was generatedusing Midjourney AI and provided under a CC BY-NC 4.0 license. access tothe diffractometer SANS2D under beamtime allocation RB2210058. 

Tilgjengelig fra: 2023-08-09 Laget: 2023-08-09 Sist oppdatert: 2024-05-27bibliografisk kontrollert

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