Room temperature ionic liquids (RTILs) represent a promising class of compounds that can address several societal challenges in a sustainable way. Being composed solely by ionic species they show negligible vapour pressure and appealing chemical-physical properties.
In the last few years much attention has been dedicated to binary mixtures of RTILs with other either ionic or molecular liquids (ML) that offer the possibility of further modulating bulk properties, thus better addressing the "designer solvent" concept.
In parallel with this opportunity, the presence of an additional compound introduces a variety of unexpected structural and dynamic features, whose exploitation can dramatically enhance the final performance, when properly mastered and understood.
Emerging evidences exist that addition of a ML can lead to complex microscopic as well as mesoscopic re-organizations that eventually affect the bulk behaviour and pave the way to novel, unexpected applications.
In this Large Research Project we propose to use an integrated, multidisciplinary approach to explore the effect of addition of selected MLs to RTILs on structural and dynamic properties at micro- and meso-scopic level and their influence over macroscopic performances. The synergic exploitation of experimental (x-ray/neutron diffraction, Raman/IR/NMR spectroscopy, rheology and synthesis of specific compounds) and computational tools will guarantee a robust understanding of complex, so far largely unexplored, phenomenologies, providing the knowledge tools necessary to lead to the foreseeing of smart performances of new designer solvents. The proposing team has well-established reputation in the exploitation of the different techniques for such a task that guarantees the success of the proposed research plan.
This Large Research Project has a high potential for delivering break-through discoveries and robust comprehension of the interactions in novel, high added value, neat Ionic liquids and their binary mixtures with MLs. Such a detailed understanding will be achieved thanks to the synergy between experimental and computational tools.
While nicely fitting into current high profile research projects from world well-renowned groups, this project aims at bringing together, in a synergic way, several complementary experimental and computational techniques, with the final goal to provide a unified description of alluring evidences of complex behaviours.
With reference to the three different lines of action that we described above, we can envisage the following outcomes:
1. Introduction of fluorous moieties in ILs is an appealing solution to join IL-specific properties with fluorine-related peculiarities. So far not many studies appeared in the literature on experimental determination of the role of such moieties on structure. Since our study in 2013, where we proposed for the first time that triphilic ILs, bringing fluorous moieties might be characterised by a highly compartmentalised morphology even at room conditions [14], this research field has evolved, but only recently some of us presented the first direct experimental evidence of such a structural organization, using neutron and NMR techniques[13]. We plan to integrate x-ray and neutron scattering techniques with NMR and IR/Raman spectroscopies to further investigate such a field. These studies will be conducted on neat ILs and on their mixtures with selected MLs such as DMSO and water, in order to probe the role of MLs in tuning IL¿s properties. Accordingly this study is expected to extend the state of the art and provide useful information for a more aware exploitation of structural and dynamic peculiarities in these systems.
2. Apart from the first study from Ludwig's[9] team that make use of IR spectroscopy to indirectly probe the transition from CIP to SIP, no further direct experimental or computational evidence exist to support this observation. Using neutron and x-ray scattering techniques we plan to obtain the first direct structural evidence of such a transition. The synergy with NMR, and IR/Raman spectroscopic techniques would provide new information that presently simply is not available on this interesting research field. Finally computational studies (both classical and ab initio) are expected to further enhance the level of understanding far beyond the present state of the art.
3. At present the state of the art in the field of mesoscopic phenomena involved in BM of ILs with amphiphilic compounds is represented by the activities from the group of Atkin [20,21] and ours [18,19] . We recently provided a robust description for selected BM of a protic IL with alcohols on the basis of a mesoscopic separated morphology that is better substantiated by evidences that other competing interpretations. Our proposed activities using the whole spectrum of experimental and computational techniques aims at expanding the range of experimentally available data sets and provide robust microscopic/mesoscopic description for these. This activity will then deliver knowledge that is well beyond the present state of the art.