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Designing functional polyoxometalate-based ionic liquid crystals and ionic liquids Yohan Martinetto, Bruce Pegot, Catherine Roch-Marchal, Betty Cottyn Boitte, Sébastien Floquet

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Yohan Martinetto, Bruce Pegot, Catherine Roch-Marchal, Betty Cottyn Boitte, Sébastien Floquet. Designing functional polyoxometalate-based ionic liquid crystals and ionic liquids. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2019, 2020 (3), pp.228-247. 10.1002/ejic.201900990. hal-02621781

HAL Id: hal-02621781 https://hal.inrae.fr/hal-02621781 Submitted on 26 May 2020

HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde Link toVoR: becitedas: To content ofthisAcceptedArticle. to ensure accuracy of information. The authors are responsible for the the VoR from the journal website shown below when to this it Accepted is Article published as a different result be may of and possible as editing. soon as Readers View Early in should online published obtain using the Digital Object Identifier (DOI) given below. The VoR will be of the final Version of Record (VoR). This work is currently citable by publication formal and proofing, editing, to prior online Article Accepted an as appears and review peer after accepted been has manuscript This Authors: Title: and ionicliquids. Designing FunctionalPolyoxometalate-basedionicliquidcrystals Yohan Martinetto,BrucePégot,CatherineRoch-Marchal, Betty Cottyn-Boitte,andSebastienFloquet Comment citer cedocument: http://dx.doi.org/10.1002/ejic.201900990 Eur. J.Inorg.Chem. Eur. Accepted Article

10.1002/ejic.201900990 A Journal of A Journal Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 Key Topic Keywords: base o focuses review in applications various 100 below temperature melting with optoelectronics in application with sometimes the of nature the materials. functional of elaboration phases crystalline liquid into components high their compounds inorganic thousand Po Abstract. Versailles, Institut Jean b) Correspondingauthor: Université Paris LavoisierInstitut Versailles, UMR8180,Université de de VersaillesSt a) Sébastien Floquet. Yohan Martinetto, liquids. ionic and Functional Designing M. Y.Martinetto, Dr B.Pégot,M. Y.Martinetto, Dr Dr Roch C. lyo Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde M. Y.Martinetto d Ionic andd crystal liquid oeaae PM compounds (POM) xometalate

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Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 chemistryand eco liquidionic biomass, lignocellulosic of use better a forcatalysis lignin and biorefinery lignocellulose on focus mainly topics research her chemistry, France. Versailles, of INRA at Bourgin prost of treatment for the ERK5 of inhibition the in research postdoctoral (NICR, for Griffin UK) R. Newcastle, Prof. of group the joined she Then, 2007. in France) NO of inhibition the and indazoles the Cottyn Betty Dr different Lavoisier the at team Ferey’s by effective spectrosc the different by of phases characterization the on focused especially but applications catalytic synthShe Versailles. Universityof the at professorassistant characterizations and synthesis the under post a for Ph.D. Lyon in IRC at Taarit Ben her during catalysis Y. joinedof theteam In 1992,she (Paris VI). Hervé supervision ofPr. for applications their and of properties fascinating the discovered she Then on FraissardVI) (Paris J. Pr. with internship an with 1989 in career academic an started Marchal Roch Catherine Dr. engineer, chemical of formation initial an After ionic chemistry, fluorine on chemistryliquid eco and focused now are activities research Paris Versailles, of (University Versailles organometallicchemistry. Paris (University assistant research of year a completed postdoctoral has and liquids, ionic for biodegradable in research Ireland) University, City (Dublin Gathergood N. Paris j he Subsequently, (University 2005. in France) liquids Orsay, ionic for synthesis assisted microwave on Ph.D. his out carried He lecturer. a is Pégot Dr.Bruce and for catalysis applications sustainable the Polyoxometalate new on of development focuses work His Floquet. of degree Ph.D. Paris of a University towards works currently He 2017. in (France) Mont of Savoie of University University the from Chemistry” Sustainable from degree Bachelor’s Grenoble chemistry his 2014, in his received He physics 1994. and mathematics chemistry, in in degree University Technical France in born was Martinetto Yohan Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde Metal Organic Framework Organic Metal - Alpes (France) in 2015, and a Master’s degree “Green and “Green degree Master’s a and 2015, in (France) Alpes .

- Boitte is a senior scientist. She carrie She scientist. senior a is Boitte - friendly chemistry.friendly - Saclay, under the supervision of Dr. Sebastien Sebastien Dr. of supervision the under Saclay, ate cancer. In 2009, she joined Institut Jean Pierre Jean Institut joined she 2009, In cancer. ate Comment citer cedocument: - friendly chemistry. This In200 129 opic methods. From the beginning of the synthesis of MIL of synthesis the of beginning the From methods. opic article

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Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 are ligands Fe {Mo as such cations monometallic [(M e 1) (Figure 1998 in centers fullerene a of discovery the Müller isopolyoxomolybdates, main the probably are 1) [M structure Linqvist The obtained. is isopolyanions named POMs of class second a anion, template a by provided heteroatom of absence in contrast, In with the properties appended ofthe design for subunit devices. the ofmultifunctional o membranes biomolecules, the as well complexes is the components the of properties physical their choice and architectures final the design The to determinant moieties. organometallic or complexes coordination heteropo reactive vacant of panel large a provides latter two the of hydrolysis controlled A 1. Figure Anderson structures: archetypical main three SiO be PO template can anions which VI), around VI) W(V, or mainly Mo(V, V(IV,V), bottom hetero namelysubclasses, two into split publicati magnetism, as such fieldsnumerousapplications in potential versatility,and they compositional properties display metal compounds discrete soluble as described frameworks, often compounds, (POM) Polyoxometalate Introduction hbt n nrai metal inorganic an xhibit Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde VI 4 lbrto o hbi fntoa POM functional hybrid of elaboration 2 4 O - 6 GeO , O - 2 up self up in supramolecular chemistry,supramolecular in E 21 lyoxometalates, viewed as inorganic ligands, which can coordinate transition metals, transition coordinate can which ligands, inorganic as viewed lyoxometalates, ons concerning polyoxometalates concerning ons 2 ) } 12 allows tuning their solubility, charge, electronic and electrochemical properties, as as properties, electrochemical and electronic charge, solubility, their tuning allows

[10 2+ which can be finely tuned at the molecular level. Owing to their structural and and structural their to Owing level. molecular the at tuned finely be can which (linker) 4 usually 4 wt E with , capability - - osiue wd fml rc o mr ta several than more of rich family wide a constitute 12] AsO , - assembly reactions of [MO of reactions assembly

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materials sciences, nanotechnology,sciences,materials an for example. Heteropolyanions are subdivided into into subdivided are Heteropolyanions example. for -

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Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 POM true on bibliography accurate precludes it and Liquids Ionic as considered formally be cannot they applications, many for interest of are they if Even materials. or salts counter adjustable assurfaces, graftedfreeimidazoliums, on or as such Ionic Liquids in typicallyused num for language of abuse an evidences papers these of investigation careful a However, hits. 550 gives knowledge of web the in entered (IL) Liquids” “Ionic and “Polyoxometalate” keywords POM to devoted be will part second A properties. and characterizationtheir to preparation their 2004 in published These 2). (seeFigure liquids ionic true or phases crystal such liquid ionic in of formation cations the either organic to lead can the hybrids, POM of versatile choice the how demonstrate to is review this of scope The bo molecularchemistryand chemistrymaterials tackle relevant to challenges today’s of the at compounds of family rich a such of overview an gives Wu Lixin vesicles usually prepare cations, organic sophisticated so to leads interactions less or more POM tertraalk within design POMs to of investigated encapsulation various been POMs, of have applications potential and strategies properties of scope extended the to Owing properties applications and their prime of clearly is cations the of nature the Nyman and Streb latter The electroneutrality! reach to cations counter to associate therefore and charged negatively they property: common one exhibit them of all compounds, of variety wide the Despite chemistry world tothe mesoscopic {Mo {Mo wheels” “big the namely POMs giant other by complemented also for catalysis nanoflasks functional as behave clusters hollow Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde e o te. n h ps dcd, ay tde hv be rpre t uiie cations utilize to reported been have studies many decade, past the In them. of ber - - 4} ad h "le eo" {Mo lemon" "blue the and 248}, cations are often mistakenly considered as spectator ions spectator as considered mistakenly often are cations based - [46] gels, Langmuir gels, cations or anchoring functions to pair with POMs with pair to functions anchoring or cations ylammonium, featuring one or two long hydrocarbon chains, by electrostatic electrostatic by chains, hydrocarbon long two or one featuring ylammonium, [38]

r rcro fr ucinlzto o mspru silica. mesoporous of functionalization for precursor or rseii hmcl transformations. chemical specific or ILs For . - 2005. The first part will focus on POM on focus will part first The 2005. hs at i i itrsig o oe ht h cmiain f h two the of combination the that note to interesting is it part, this - - Comment citer cedocument: called Surfactant Encapsulated Clusters (SEC), which can be used to to used be can which (SEC), Clusters Encapsulated Surfactant called Blodgett films Blodgett This article . [40]

domains are relare domains is (

see Figuresee 1 protected , [41 - - 43] 368 by

modified electrodes, modified }, which expanded the frontiers of inorganic inorganic of frontiers the expanded which }, copyright. ) . [21, [21, 31] [39] atively new since the first publications werepublications first the since atively new

All This family of polyoxomolybdates was was polyoxomolybdates of family This rights cation - . Such pairing lead pairing Such . ae fntoa mtras The materials. functional based - based Ionic Liquid Crystals, from Crystals, Liquid Ionic based reserved.

importance for designing their their designing for importance

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materials for catalysis, for materials [47] -

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Abbreviations are those used in the literature by their authors. their by literature usedin the those are Abbreviations article is

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(a) Arrangement of molecules or clusters in nematic or lamellar smectic lamellar or nematic in clusters or molecules of Arrangement (a) F no 2D into igure 3. igure

and their and hs omd xiis anisotropic exhibits formed thus

from Lixin Wu Lixin from n shape n - [51] atcs Depending lattices. identification identification -

ie oeue o dnrtc opud i wih oeue interact molecules which in compounds dendritic or molecules like The Nematic phase (N) corresponds to the least ordered mesophase. It mesophase. ordered least the to corresponds (N) phase Nematic The Comment citer cedocument: ,

This the assembly of cations surrounding the POMs is not randomized. not is POMs the surrounding cations of assembly the article

et al et in the orientation of the mole the of orientation the - . is is more difficultmore is [51] Ray diffraction since the diffraction lines (00l) are easily are (00l) lines diffraction the since diffraction Ray

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with the permission from Wiley.) from permission the with o n h ), rectangular (Col rectangular ), by h pcig oe te ounr hss are phases columnar the mode, packing the copyright. shape . However, Finally, the columnar phases results from from resultsphases columnar Finally,the All rights ul cmail wt te schematic the with compatible fully r ), oblique (Col oblique ), reserved. Note that even if the POMs are POMs the if even that Note cules within the layers as shown as layers the within cules one can distinguish smectic A, smectic distinguish can one

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the difficulty to work with hybrid POMs, especially in terms of purification. We We purification. of terms in especially POMs, hybrid with work to difficulty the (L) . In contrast, Polarz contrast, In . et al. et n PW [58] [52 11

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of the literature.

n te rai ctos ouiie i ognc ovn, usually solvent, organic in solubilized cations organic the and of article n arn iognc clusters inorganic pairing in

Song, Guo and coworkers and Guo Song, 16 , which offers a large panel of materials tuned by the design the by tuned materials of panel large a offers which , H is et 33

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Society of Chemistry.) of Society All rights a , n tihoerc proportion stoichiometric in ,

TBA [58] the only example of example only the reserved. or POMs POMs or

resulting from a micellar self micellar a from resulting who synthetized dendritic synthetized who h SC s hn sltd by isolated then is SEC The

or not or salt ong, Guo Guo ong, modification (Figure 2) (Figure .

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Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 Wu translate or bonds hydrogen producing m of nature the of protonation influence POM the of as well stabilization as the POMs, and nature the explored they particular, formation, In mesophases. the influence can which date to up 2005 pion first its since Wu Lixin of group the by developed format The POMsPairing cation functionalized with with mesogenic functions following sections. the in developed be will pairing ion on based approaches different The found. be must POM the between compromise Cadot by example in these solution, are in even but, They neglected often cation. organic and POM between interaction also the account is into it take Finally, to solid. necessary the within organization the favor thus and parts organic between which cyanobiphenyl parts organic as the on functions, such mesogenic called functions groups, aromatic introducing by accomplished usually is point occur. must POM or bet cluster inorganic each interactions around chains Secondly, crystals. liquid get hopefully to needed is the cluster of surface the and chains organic the crystal of surface liquid the between get ratio to minimum A satisfied phases. be must points key several approach, chosen the Whatever interaction thesolid within term the of bands vibration stretching antisymmetric and symmetric the since used are chain alkyl analysing allows state solid the in allowscharactersolution also can Small and Calorimetry Scanning comb the by least at investigated are Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde inal t al. et d be be -

CH by tre t ascae n zbnee otiig ainc ufcat ald 1 (see L1 called surfactant cationic containing azobenzene an associate to started ion of POM of ion help state 3 number of number

and of the the of and ful to understand the fo the understand to ful , their symmetry or the or symmetry their , W ad i claoaos ae studied have collaborators his and Wu ,

t al. et - Comment citer cedocument: based liquid crystals by association with mesogenic cations has been has cations mesogenic with association by crystals liquid based

izing the interactions between the cations and the POM, whilePOM, FT and the cations izing theinteractions between the papers we will will we papers strength of the interaction and the freedom of the cation the of freedom the and interaction the of strength

This . - ih elrt compounds. Keplerate with [60] CH article

2 - capabl

- groups depend on the symmetry of the molecules and the the and molecules the of symmetry the on depend groups angle X angle is

protected the organization within the solid when cations bearing bearing cations when solid the within organization the nto o Plrzd pia Mcocp, Differential Microscopy, Optical Polarized of ination e r

influence of the the of influence try to summarize in this section. this in summarize to try m the inf the of - a Ray Diffraction. Ray by tion of mesophases. NMR in the solid state or in or state solid the in NMR mesophases. of tion nrdcn chirality introducing teractions can be relatively strong as shown for for shown as strong relatively be can teractions copyright. l uence of the size, the of uence All eering work published in 2005. From 2005. in published work eering rights [61] introduction of functions capable of of capable functions of introduction sgnc ain, hi sz, their size, their cations, esogenic

In the field of liquid crystals, t crystals, liquid of field the In hrfr t bid C hs, a phase, LC build to Therefore ey rcsl mn parameters many precisely very reserved. NMR and FT and NMR will create create will .

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] that the thermal behavior of these materials is driven by L1. The three POMs being threePOMs L1.The by driven is materials these behaviorof thermal the that 12 3

4 - 2 12 - - f h pooain o protonation the of

[PW , O [SiW dutbe ain wr pie wt te or Os [Eu(BW POMs four the with paired were cations adjustable and O 40 40 10 ].2H s ere

]Br N were detected by DSC and in each case two different type different casetwo each in and DSC by detected were [SiW 12 quid crystal materials. crystal quid 12 + r [62] O 13

e b vral tmeaue FT temperature variable by med 3 O 2 dniid y X by identified

ih = , , 0 r 12. or 10 8, 6, = n with .2H [Tb(SiW O were obtained. For [SiW For obtained. were O 40 r saiie b hge cags and charges higher by stabilized are 40

12 ]Br In the following of this work, the same cation L1 was combined with combined was L1 cation same the work, this of following the In ] Comment citer cedocument: O 3 2 - O, ad h Ander the and , 2 40 This [Tb(SiW .2H ] 4 - 11 article s lai salt alkali as , 2 s O and only SmBfor phase O

were found very similar to those of cation L1 alone, which which alone, L1 cation of those to similar very found were (L1) n 39 is ) 11 h poete o te 1 ain n em o competitive of terms in cation L1 the of properties the 2

protected ], ], - il wih erae fo 15 C o 6 °C 164 to °C 185 from decreases which rials 3 O a dfrcin n plrzd pia microscopy. optical polarized and diffraction ray [PW 39 (L1) ) [64] 2 ] 12 o drvtv [ZnH derivative son 13 11 by O In 2008 also, they changed the L1 catio L1 the changed they also, 2008 In - s [Eu(PW , [Eu(PW ,

40 [65] copyright. ra acids. as or ].4H 12 12

s en n iue 2 Figure in seen As O O 40 40 of these of 2 O, 11 ] ] All - 4 4 R esrmns n the and measurements IR 11 O - -

POM. The authors carefully analysed carefully authors The POM. rights O derivatives different derivatives 39 s in the low the in s 39 [64] ) (L1) 2 mization of surfactant which play play which surfactant of mization )

], and ], (L1) by reserved. three salts allowed to investigate to allowed salts three 2

] In the presence of protons of presence the In 11 4 6 strong [SiW - Mo 2 , and [EuW and , 12 (HL1)

O (L1) SmC and SmA phases for phases SmA and SmC 6 40 O 12 or e materials new Four

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2 - [EuW ] , h to og organic long two the to 9 to [SiW 40 interactions 3 which indicated that that indicated which - ].2H .

s h ojcie of objectives The 10

- of smectic liquidsmectic of

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]Br ], ], - region 11 . [62, 63] [62,

. O different n by the by n between between 2 smectic Careful 39 .2H ) , 2

The The ] For 2 but the the 15 O, 11 - ,

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde additional 12 - 10 Isotropic liquid was observed by DSC. Interestingly, the transition temperature transition the Interestingly, DSC. by observed was liquid Isotropic drives the high temperature transitions. In the same work the effect of the nature of the the of nature the of effect the work same the In transitions. temperature high the drives O O ) and the authors studied the effects of the length and the number of alkyl chain on chain alkyl of number the and length the of effects the studied authors the and ) 40 11 11 13 b at 36 ] n h sld state solid the in O [Eu(PW [Eu(SiW enzoic acid function of CDDA of function acid enzoic 3 ] - 9 39 ad [ZnH and , h ed f n akl chain alkyl one of end the - [Eu(PW , ) pyridine derivatives pyridine provides a new strategy to get liquid phases. They phases. liquid get to strategy new a provides 2 ] 15 - -

3 11 assemblies exhibiting supramolecular liquid crystal properties (SmA, SmB (SmA, properties crystal liquid supramolecular exhibiting assemblies was associated to four four to associated was 11 [PW O O 39 39 11 Comment citer cedocument: ) 12 6 ) 2 that the shape shape the that Mo 2 O ] exhibited a sequence Solid sequence a exhibited ] O ad the and ] This 39 40

6 ) n in and ] and (CDDA) and ] O 2 article ] 24 11 ] -

3 bearing for the main part of them long alkyl chains, chains, alkyl long them of part main the for bearing - is n [Eu(SiW and

done

ih h sm cto C cation same the with protected h liqui the the terminal benzoic acid triggered the organization of organization the triggered acid benzoic terminal the and the surface char surface the and o ie h cto CDDA cation the give to with L1 cation, L1 with type of type w mtras (CDDA) materials two + . , the resulting multi resulting the , 4 by [SiW compl was system This cytl phase crystal d copyright. - SmC 11 12 cations C cations O O h the increase of the tail length tail the of increase the h - 39 SmA 40 All ) - ]. 2 SmA ] rights [67] [62] 13 - - . In a next step of step next a In Iso. L Iso.

n [66] By formation of H of formationBy it means that the low temperature temperature low the that means it BphC - [Eu(BW reserved. ge density ge

Iso, while (CDDA) while Iso, 8

n te uhr eiecd the evidenced authors the and BphC - ept te ly can are chain alkyl the Despite components reverse micelles micelles reverse components uminescence properties uminescence 10 + introduced a benzoic acid benzoic a introduced N icated icated

10 11 ersne i Fgr 2 Figure in represented 13 +

N O [Eu(SiW with n = 6, 8, 10 or 12 12 or 10 8, 6, = n with of the POM the of + 39 Te eune of sequences The . ) by the introduction the by 2 - ] his work, Wu and Wu work, his bonding contacts. contacts. bonding 15 9 [EuW - - [BW , bonds with the with bonds 10.1002/ejic.201900990 11 - Solid2 9 ht ordered that O [EuW , while the the while , 39 10 s play an play s ) O 2 12 and ] s - 36 O 10 SmC to the to

were from to ] 40 O ] 36 4 12 - ] - . , ,

10 (Reprinted from (Reprinted 12 - [Mn Nematic O 40 Top: Structural representation of POM of representation Structural Top: design 4 ] (H 5 - [SiW , 2 O) - l s ad the and Iso a of example first the is it and POMs with observed usually are phases ar

2 of the cations induces the formation of such a nematic phase. nematic a such of formation the induces cations the of (VW tcmn wt te he POMs three the with ttachment Wu a 11 ges of the resulting SEP resulting the of ges - 30 °C) according to a process driven by the cation, while the Nematic to Nematic the while cation, the by driven process a to according °C) 30 O - 12 and 12 9 et al. et 39 O Comment citer cedocument: Co(H 34 ) This [68] 2

] temperature of the the of temperature a proposition of the org the of proposition a

, once again in with the permission from Wiley.) permission from the with 2 article

O)] se B (see In 2013, Wu Wu 2013, In 6 is -

n [Mn and protected - 12 on Figure 2) onto the surface of the three POMs POMs three the of surface the onto 2) Figure on 12 - 1 at 130 at 1

- by agreement withaPOM agreement 1, POM 1, 4 copyright. (H t al. et hs transition phase 2 a

O) °C nization of the resulting nematic phases; Bottom: Bottom: phases; nematic resulting the of nization

- 2 and POM and 2

2 n te eutn aiorpc surfactant anisotropic resulting the and (a), SEP (a), (VW

All kept us this work by by work this us kept rights 9

- O 12) - reserved. 34 2 at 127 at 2 ) - 5 2 3 combined by Wu and coworkers coworkers and Wu by combined 3 [BW ] 10 S - . olid - [68] dependant process.

12 °C - O hp,te B the shape,

h cto aoe was alone cation The 40 (b) and SEP and (b) to to ] eai appeared Nematic graft 6 ° fr (B for °C 168

Of 10.1002/ejic.201900990 n T ing

course, - - 3 at 100 at 3 12 cation cation 12 - shape shape

the the

°C 13

s -

Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 2009. mesogenic non associating by of capable them renders subphase. distinct own their which into segregate to POMs the of surface but the form, anisotropic an into deformation at cations the of mobility non with obtained be also can phases favored is mesophases of organization the if Even POMsPairing non with work this withPOMs.extend diversit their account into taken and, POMs with used been [Re cluster the with associated imi Y. “ cyanobiphenyl with functionalized cations successfully section. this charges, fill and to size authors of other identify not did Nev we cations, sophisticated such of task that the constitutes hard probably tothe due ofPOMs, In thedomain POM multifunctional crystals crystal combining property, towards chiralitychiroptical liquid switches. luminescence, and route the opening thus temperature, the with (LCh) material the Furthermore, interactions. electrostatic through POM the to transferred is group cholesteric dichroism circular by demonstrated authors the material, t less former, the for to SmA temperature:rangeof wide a in thus and mesogenic be identified indeed to were phases crystalline Liquid mesophases. of known formation are cholesterols chiral, be to addition [PW POM monovacant the of LCh called surfactant ammonium containing and 2017 in published papers recent two Finally, clustomesogens Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde aoim at (e cto TP cation (see salts dazolium oad n cwres et p hs ok y rprn bly triphenylene bulky preparing by work this up kept coworkers and Molard e rtheless, in the chemistry of metallic clusters, which can be compared be can which clusters, metallic of chemistry the in rtheless, [73]

hy synthe They combined the cluster [Re cluster the combined ”

13 ossig wthbe antclmnsec properties. magnetic/luminescence switchable possessing [Eu(SiW

s Molard Molard Comment citer cedocument: ized hybrid materials by ionic association of the Preyssler type type Preyssler the of association ionic by materials hybrid ized - mesogenic cations This 11 article 11 O

6 O t al. et Se ain wt a O ws eotd y ut, Faul Kurth, by reported was POM a with cations 39 39 ) 8 is 2 ] 2 (CN)

+ 7 ] displayed intrinsic luminescence that could be adjusted be could that luminescence intrinsic displayed ] protected

- ,

- [69] on Figure 2), which led to a columnar phase when when phase columnar a to led which 2), Figure on mesogenic cations. It can be due to versatility and the and versatility to due be can It cations. mesogenic probably 6 Se 6

] or the Eu the or

4− also to the propensity of POMs and organic and POMs of propensity the to also 8 (CN) by . groups (see cation KAT cation (see groups [72] + copyright. [51]

in Figure 2 which was used for encapsulation for used was which 2 Figure in

These cations, to our knowledge, have never never have knowledge, our to cations, These 6

en isie b te ok f ii Wu Lixin of work the by inspired being ] The first ex first The n− - containing POM [Eu(SiW POM containing

(n 08 eotd h ue f cholesterol a of use the reported 2018 ih eoei ctos lqi crystals liquid cations, mesogenic with All = rights

- spectroscopy that the chirality of the the of chirality the spectroscopythat ordered layer for the latter. For each Foreach latter. the for layer ordered 3, 4) with 4) 3, reserved. a mples of mesophases obtained obtained mesophases of mples ies i cud e neetn to interesting be could it , the +

in Figure 2) Figure in tetraalkylammonium multi f

or both materials both or to P to [71] 11 - O 10.1002/ejic.201900990 step -

OM in terms in OM ae liquid based 39 F. - ) substituted substituted rigger the the rigger

o design to ] synthesis Camerel, t al. et 13 ca - . [70] tions

In in 14

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde + +

, iehlieaeyamnu (DHDA dimethyldihexadecylammonium ), of the cations size allowing to propose the lamellar organization depicted in Figure in depicted organization lamellar the propose to allowing size cations the of trioctadecylmethylammonium cation tail triple and ) o ad ie iw o te ryse tp ain [EuP anion type Preyssler the of views side and Top 5 W dn o te ly can lengt chain alkyl the on nding 30 O Comment citer cedocument: 110 This ] 12

- article

Fgr 6) (Figure 16 is TA

protected + ) and ) an ammonium cation bearing one C one bearing cation ammonium an by octadecyltrimethylammonium (C octadecyltrimethylammonium copyright. soitd ih ige al cations tail single with associated 18 NEO + All . H h. ad dimethyldioctadecylammonium and ) rights + 3 + , dimethylditetradecylammonium ),

5 ge tasto temperature transition igher W ain n iue ) ard with paired 2) figure on cation reserved. 30

(C O 110 18 ] MA 12 -

and lamellar organization organization lamellar and

from Kurth, Faul Faul Kurth, from + ). In ). each case each 18 10.1002/ejic.201900990 18 TA

- alkyl chain chain alkyl 60.6 °C to to °C 60.6 + ), double ), , DSC, DSC, , et al. et th the th s

are 15 [73]

Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 so the border not two domainsis between these POM that demonstrate and systems ILs of in used two usually cations tetraalkylammonium examples with obtained These only phase. the crystal date, liquid to lamellar constitute to publications cubic from phase the counter crystallograp of modulate nature cubic can the on cation displayed playing that chains demonstrate which alkyl state, solid shorter the in two arrangements the with obtained salts the TOAfor °C 28.2 and °C 89.8 at found temperatures (TDA [SiW of salts tetraalkylammonium of series a preparing by work this up kept coworkers Wu ILs. (TOA) thus and TOA a associates interestingit is since result This Figure7). (TOA) (TOA) materia the of properties the pairing cation tetraoctylammonium studiedwith[PW coworkers and Wu work, this of following the In [PMo the of transition the finally [PMo between the in the POM around cations the of organization the delay thus and motions free reduce interactions influe notably former The the and POM the aroundIn crowding particular the results. these severalexplaining the influence parameters of decompo others two the while respectively, °C, 163.9 and °C 181.4 at phase crystal liquid B smectic a towards transition C phase a displayed the only Interestingly, phase. crystal transition the decrease to contribute also and chains alkyl domains hydrophilic the of collapsethe provoke canmesogenic, it non is chain althoughTEO Besides, size. andshape they since POM the of charge the of influence the studying notably allowed Kegging Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde 12 + 4 5 3 ). O [GeW [BW [PW [60] - 40 type anions [PMo anions type a ]

4 With the two longer alkyl chain, lamellar LC phase were obtained with transition with obtained were phase LC lamellar chain, alkyl longer two the With - 12 ih ere f reo wt a oaial rgd O ad h to materials two the and POM rigid polarizable a with freedom of degree high 12 akl hi big uy (TBA butyl being chain alkyl , 12 ( Cristal Liquid O O 12 O 40 40 O 40 dd o ehbt hrorpc C eair (TOA) behavior, LC thermotropic exhibit not did ] ] displayed smectic LC phase above 80.2 °C and 115 °C, respectively (see respectively °C, 115 and °C 80.2 above phase LC smectic displayed ] strength of interactions of strength 40 ] and (TOA)and ] ] 3 -

n ctos hn ih h aaoos ugtc O [PW POM tungstic analogous the with than cations and Comment citer cedocument: up This 12 cs h ntr o te hs. o te atr tog POM/cation strong latter the For phase. the of nature the nces n etn, otiue o h pcig n cnomto o the of conformation and packing the to contribute heating, on O article LC 40 5 [BW ] ) 12 3

- , [PW , is O phase

protected 40 12 ] O 3 - 40 12

. For instance, the electrostatic forces are stronger stronger are forces electrostatic the instance, For .

salt is so delayed that it decomposes before melting. before decomposes it that delayed so is salt between the POM and the cation are of importance. importance. of are cation the and POM the between ] can be be can ] O 18 by 40 NEO 12 ] copyright. 3 O - significant ,[SiW + sed before melting. The authors highlighted authors The melting. before sed , ey (THA hexyl ), 40 3 ] + thus 3

+ - , [GeW

at o [PW of salts 12 and TDA and All O regarded, from the authors, as ordered ordered as authors, the from regarded, rights 40 . ] 4 12 + - reserved. eprtr rm oi o liquid to solid from temperature , and [BW and ,

O cation with four flexible groups flexible four with cation + 40

salts respectively. In contrast contrast Inrespectively. salts ae lqi crystal liquid based + ] , cy (TOA octyl ), 4 - 12 , or[BW O 40 12 ] O 3 -

40 4 12 n [BW and all [GeW ] 5 O - . [74] have have 10.1002/ejic.201900990 40 + ] 12 5

) or decyl decyl or ) 12 This series This - O . O [75] the same same the 40

40 12 ]

phases phases and ] While 3 O -

40 and hic hic ] 16 ls 5 -

i.e. (a) The tetrahedral conformation of TOA of conformation tetrahedral The (a) 5 ain hc ws soitd ihr o h rr Waugh rare the to either associated was which cation O [BW 58

] [MnMo smectic phases with transition temperatures around 50 °C and similar interlayer similar and °C 50 around temperatures transition with phases smectic 12 12 two O - , [77] 40 - B ] at 45 °C on cooling from isotropic liquid (100x). (Reprinted from Wu from (Reprinted (100x). liquid isotropic from cooling on °C 45 at ] POMs POMs o Wang also contribute also Wang o

r o h pooestv O [PW POM photosensitive the to or 9 O 32 Comment citer cedocument: ]

6 This optical polarized microscope. (TOA) microscope. polarized optical [MnMo -

n [CeMo and article 9 is O

protected 32 ] 6 -

12 n [CeMo and O d to this field. They focused their attention on attention their focused They field. this to d by 42 copyright. ] + 8

cation; (b) Keggin polyoxoanion Keggin (b) cation; - , [76]

o h hxvcn Germanomolybdate hexavacant the to All 12 O rights 11 42 O 4 ] [GeW 8 39 reserved. -

RhCH nrpe wti te DODA the within enwrapped 12 O 40 - 2 type ] at 85 °C on heating, and (f) (f) and heating, °C on 85 at ] CO 2

H] n Silverston and 5 - . in the space the in [78] 10.1002/ejic.201900990

et al. et o te first the For +

alkyl in the the in alkyl [60, 75] [60,

- filling filling -

type type with the 17 +

Accepted Manuscript Version postprint correspondance) (2019). Designingfunctional polyoxometalate-based ionicliquid crystalsandionic liquids. European JournalofInorganicChemistry European Journal of Inorganic Chemistry, 2020 (3),228-247. , DOI:10.1002/ejic.201900990 are cations the of chains alkyl the that and cluster anionic the around organized randomly parameters self a them and be cations association ionic the on based materials new eight a strategy, this Using ethanol. of addition by were phase materials chloroform target from the precipitated that and phase aqueous the from POMs the extract fully to used cati organic of excess large very a that excepted keplerate Wu Lixin of Waals that to der Van selected of occurrence the force first to similar was proceduresynthetic Thecations. counter of largenumber the betweeninteractions aim in we charges high their of cations, because mainly the on [Mo function mesogenic POM subsequent the prepare C from ranging chains alkyl simple with use to cations chose we Versailles, in developed we work the In crystalwas phaseL characterized for of formation chloroform of solution mixed self the study to aim [Eu(SiW (L’ benzyl]imidazolium tris(octadecyloxy) cations, imidazolium POM true a of characteristic [PW were performed on l obser was phase crystal liquid A smectic a the towards transition For 3). Figure (see layer cation DODA between formed cluster the of angle of variation the with agreement in increase, temperature with distance interlayer of decrease a observed they preciselybut determined not were phases smectic the of nature The °C. finally116 at liquid isotropic and °C 82 and 75 61, at phases smectic different 3 to state solid from transitions german The charges. of difference the despite spacing Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde 132 11 O O

(DODA 39 372 11 RhCH O (CH h 39 [Mo -

organization in lamellar mesophases was evidenced. From the structural structural the From evidenced. was mesophases lamellar in organization a ) and the intercluster distance distance intercluster the and 2 3 ] + 2 aelr hs i te oi sae o a for state solid the in phase lamellar COO) 13 ) and one step one and ) CO 132 - , [EuW , O this material. Note that in the same study material.the this in Notethat 2 H] 372 - 30 assembly behaviors and aggregates morphology of these hybrids in in hybrids these of morphology aggregates and behaviors assembly Comment citer cedocument: 5 i.e. (CH (H -

10 This 2

was studied and revealed only a melting point at 73 °C, °C, 73 at point melting a only revealed and studied was O) O 3 - ihr 1,3 either COO) IL. Finally, one can cite also the recent work of Tan, who paired paired who Tan, of work recent the also cite can one Finally, IL. 36 article 72 - ] - ] - ae mtras n lre scale. large a on materials based 9 made alkyl made 42 methanol. - , and , - a is 30 and [Mo and t

ter protected (H 4 [SiW

- 2 K icaeyiiaoim (L dioctadecylimidazolium O) aeil (DODA) material eplerate [Mo eplerate 12 7, 80] [79, 72 12 - by 132 ] [C methylimidazolium to C to O + a 42 wt [SiW with ) copyright. hex 40 - S

]. a be obtained. been has

60 , we demonstrated that the cations are not not are cations the that demonstrated we , 20 [80] The study of these hybrids revealed the the revealed hybrids these of study The O , a strategy which offers offers which strategy a , 312

All 132 (SO l hs hbis n a mci l smectic a and hybrids these ll rights O we 1 tween o 4 372 oydt cmon ehbtd 4 exhibited compound molybdate 5 ) 12 [PW n , the tetraheptylammonium salt of thetetraheptylammoniumsaltof , reserved. (H (CH O ved at 36 °C and optical studies optical and °C 36 at ved dimethyl 40 2 11 O) ] 3 4 - O COO) - methyl 132 [Eu(SiW , n

[81] 39 + mim] o aac te ak of lack the balance To ) or or ) RhCH - 2n

n te O wt the with POM the and ons in chloroform was chloroform in ons dioctadecyl For the major part of of part major the For ] 30 (12+2n) + - (H 3

cations substituted substituted cations 1 - 2 alkylimidazolium 2 CO - the O) methyl - 11

(n = 23 = (n 10.1002/ejic.201900990 - 72 O 2 type POMs POMs type possibility to to possibility H] ] 39 42 ammonium )(H , -

series of of series 3 with the with a phase phase a - 2

[3,4,5 O) or 30) 30) or iquid iquid 2 ] 18 5 to - - ,

ed ) nanocrystals and {Mo and nanocrystals ) For the former, they used used they former, the For O +

372 36 favoring Van der Waals interactions between alkyl chains of cations. In this case case this In cations. of chains alkyl between interactions Waals der Van favoring - uh iud rsa poet. nte eape f ey iia cmon obtained compound similar very of example Another property. crystal liquid such - cations interacting with these nanoscopic systems. Interestingly, the lamellar lamellar the Interestingly, systems. nanoscopic these with interacting cations 3 ye lses ih surroundi with clusters type (NH - (CH alkylimidazolium cation byDODAcation alkylimidazolium dependent Polarized Optical Microscopy revealed the formation of a birefringent a of formation the revealed Microscopy Optical Polarized dependent ioeydmtyamnu (DDDA didodecyldimethylammonium 4 3 ) COO) 6 [Mo [83] 132 30 nterestingly, t nterestingly, Comment citer cedocument:

(H O In this case, the alkyl chain length is probably too small to get liquid get to small too probably is length chain alkyl the case, this In [82] + 372 This

2 cations within the sheets is maintained with an increasing value of of value increasing an with maintained is sheets the within cations O)

[33] (CH article 72 - 132} surrounded by DDDA by surrounded 132}

56 ] The larger charge of the capsule allows associating more more associating allows capsule the of charge larger The 42 3 (NH We demonstrated that the ionic salt salt ionic the that demonstrated We COO) - hs opud o rpr hxgnl raie lyr on layers organized hexagonal prepare to compound this is by the the by

protected he overall structure as well as the stoichiometry of this this of stoichiometry the as well as structure overall he 4 ) 16 g DODA ng 30 [Mo (H “ classical ufrtd n [Mo one sulfurated by 2 O) 132 asml o shrcl . n mgeie ( maghemite nm 6.2 spherical of oassembly copyright. + 72 S

cation bearing two C bearingtwo cation 60 ] ∙ + O 75H

” within the layers of the mesophase. The The mesophase. the of layers the within 312

+ All ) 2

- (SO O self O encapsulated rights {Mo + 4

) - reserved. - 30 l a in Finally, cations. rsaln ntr of nature crystalline 132} keplerate compound compound keplerate 132} - organizes into a layered liquid layered a into organizes (H 132 et 2 O O) al. 312

72 [41, 42] [41, 18 Mo S ]

60 ∙ alkyl chain per cation, cation, alkyl per chain 15H (SO 132

and by Barboiu by and

2 4 was reported by by reported was O upto ) 30

10.1002/ejic.201900990 instead of oxo of instead oe f them of none (H the sample sample the 2

ast part of part ast O) Replacing Replacing

34 Å. other 7 2 ] 72

- [84] the

19 as (  et et x - -

COO) with the permission from the Royal Society of Chemistry) of Society Royal the permission from the with article 4 ) 30 ] (right at 200 °C; Bottom: schematic representation of th of representation schematic Bottom: °C; 200 at (right ] 30 is ]

protected to h’ for for h’ to by copyright. (DODA) 36 + (NH

cations are distributed within the layers. The The layers. the within distributed are cations All 56 4 rights (NH ) 6 [Mo 4 reserved. ) 16 132 [Mo O 372 132 (CH S 60 3 O COO) 312

(SO 30 ] (left) and and (left) ] 4 10.1002/ejic.201900990

) 30 ]. ]. (Reprinted (Reprinted e Liquid 20

It possesses a large anionic pocket of about 1 nm in diameter, which is able to to able is which diameter, in nm 1 about of pocket anionic large a possesses It The cyclic superlacunary anionic POM [H POM anionic superlacunary cyclic The

olwn te ae taey w coe o obn te ring the combine to chose we strategy, same the Following . The materials have been analys been have materials The . .

behavio [ {Mo Comment citer cedocument: This 4 nced a dipolar interaction through space between the phosphorous the between throughspace interaction dipolar a nced O [ [ C C u article 4 r with a transition temperature ranging from from ranging temperature transition a with r S n n mim mim 4 - (H shape cluster [Mo cluster shape is

2 protected ] ] O) + + akl hi rnig rm C from ranging chain alkyl , shape anisotropy instead of the spherical keplerate keplerate spherical the of instead anisotropy shape salts evidenced a perfectly linear dependence with the the with dependence linear perfectly a evidenced salts 3 (OH) ng the POM with 19 to 26 organic cations were were cations organic 26 to 19 with POM the ng by 2 copyright. } 2 (P 8 ed by usual techniques. In particular MAS MAS particular In techniques. usual by ed W - 154 a pten rvae te omto of formation the revealed patterns ray All 48 (NO) O 7 rights P 184 8 W 14 )] reserved. 48 36 O O - 448

184 Fgr 9) (Figure H - ] ae lqi cytl, the crystals, liquid based 8, 87] [86, 14 33 (H - 12

represents an attractive an represents

2 o C to O) +

and 70 Additionally, - 3.5°C to +46.2°C +46.2°C to 3.5°C [89] ] 20 28 ion of various various of ion ad DODA and , th and Faul, and th [ 10.1002/ejic.201900990 -

C with DODA with with n of different of mim ] - + alkyl shape shape salts this this [73] 21 + + - .

tween the columns (see Figure 11 Figure (see columns the tween Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde Following this idea, they succeeded to design columnar hexagonal arrangements mainly mainly arrangements hexagonal columnar design to succeeded they idea, this Following (C An original promisingAn original approach - 16 based crystals ionic liquid new with arrangements mim) 23 + -

Top and side structural structural side and Top 1 at 240 °C (d), (C (d), °C 240 at 1 and Cs and - like complex complex like (Reprinted from Floquet, Terazzi Terazzi Floquet, from (Reprinted this strategy constitutes constitutes strategy this + , within functionalized 15C5 or 18C6 crown ethers (see Figure (see ethers crown 18C6 or 15C5 functionalized within , Comment citer cedocument:

for compound (C compound for 8 W DODA This 48 } moiety is depicted in blue and pink polyhedra, molybdenum in green, green, in molybdenum polyhedra, pink and blue in depicted is moiety } article 18 omd ewe te rw ehr ad h akl, hl the while alkali, the and ethers crown the between formed 31 mim) 19 P{ - 1 at 203 °C (a), (a), °C 203 at 1 is 1 views of the perpendicular isomer of of isomer perpendicular the of views H} Hetcor CPMAS NMR spectra of of spectra NMR CPMAS Hetcor H}

). Even if this family of clusters does not formallybelong not does clusters familyof this if Even ). 24 protected - 1 at 240 °C (e) and (C and (e) °C 240 at 1

by by 16 mim) encapsulating a by very interesting perspective for developing new new developing for perspective interesting very copyright. 23 - ( et al. et of value averaged the of variation Linear Inset: 1; n C

12 in [C in mim) [90] All

n with the permission from the Royal Society Royal the from permission the with . rights mim]

20 akali counter - 1 at 240 °C (b), (b), °C 240 at 1 mim) reserved. +

cations; Side view of the the of view Side cations; 24 - 1 at 240 °C (f); Right: SA Right: (f); °C 240 at 1 d the polyanion 1 within the the within 1 polyanion the d DODA 1

in polyhedral and ball and polyhedral in - cations ( 19 C - 14 1; Middle: Middle: 1; mim) 10.1002/ejic.201900990

26 - 1 at 240 °C 240 at 1 Schematic Polarized 10 - - ) XRD and . [91, 22 -

n Cs and 6 ] 2 - . [91,92] +

one cation counter

Comment citer cedocument:

This article s is

X 14 ] 2 -

(X (X

and = 10.1002/ejic.201900990 l B, ) and I) Br, Cl,

coworkers to to coworkers 23

- 1. Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde 2 Synthesis of true of polyoxometalateSynthesis - yteie cmlxs and complexes synthesized

POM : Representation Representation : to hybrid salts with higher melting points. POMs, IL POMs, with higher meltingto hybridsalts points.

- based Ionic Liquids Ionic (POMbased Comment citer cedocument: of 15C5 crown ether derivatives, A derivatives, ether crown 15C5 of een all the types of association of POM with organic cations, we can we cations, organic with POM of association of types the all een

This C wie L cation IL while °C, article

yrd self hybrids is -

ILs. protected - based ionic liquids (orliquids POM ionic based O

(c,d). - ionic liquids liquids ionic

- - ragmn i te iud rsaln phase crystalline liquid the in arrangement ILs) by

Rpitd from (Reprinted copyright. counter -

- ae PM oi sld ntd IL noted solids ionic POM based POM@IL and POM and POM@IL All - (POM cations with POMs, generating an an generating POMs, with cations 2 rights Mo - ILs will be used for salts displaying salts for used be will ILs 6 X reserved. M 14 - ILs) -

olard olard transition metal cluster compound compound cluster metal transition POMs or POM POMs ” and “ionic liquid” words in words liquid” “ionic and ” - ILs. Many studies report the report studies Many ILs. - ILs) is simply POMs ILs) POMs issimply

t al. et (a,b); (a,b); - IL@IL, respectively. In respectively. IL@IL, [91] DSX n WAXS and SAXS 2D

with the permission permission the with - ILs solubilized 10.1002/ejic.201900990 . [40,93 - Os are POMs .

- Polarized - ILs. For ILs. 97] paired

Even 24

Nomenclature of POM of Nomenclature

DC o sals h gastasto tmeaue ( temperature transition glass the establish to (DSC) solvent: as used(IL) . Furthermore, depending on necessity, other measurements can provide more more provide can measurements other necessity, on depending Furthermore, .

te s o Dfeeta Temc nlss TA o D or (TDA) Analysis Thermic Differential of use the e - IR spectra, UV spectra, IR - Comment citer cedocument: ILs are mainly prepared by exchanging protons or the alkali counter alkali the or protons exchanging by prepared mainly are ILs This - based organic ca organic based article ic analyses (TGA) are of interest to characterize the number the characterize to interest of are (TGA) analyses ic is

- protected Vis spectra and by NMR techniques in the solid state or state solid the in techniques NMR by and spectra Vis Real Salt oforganicSalt ILcations and POM Acid or POM I onic tionsdefinitions: and by .

copyright. an excess of the organic cations as done for the the for done as cations organic the of excess an IL POM L iquid with POM anions withPOM iquid D - POM in IL in POM efinition anions - All POM salts in IL salts in POM ILIL in -

L hc pre which IL rights

reserved.

- IL T are g cipitates or forms a new new a forms or cipitates ,smtmsdfiut to difficult sometimes ),

physicalpropertiessuch

dried and analyzed. A analyzed. and dried

feeta Scanning ifferential he readers as shown shown as readers he Gl et otn an (often vent ass transition 10.1002/ejic.201900990 < 100 > 100 < 100

°C °C °C

d to to d 25

Mo Examp .

2 ( ° r P or O) eot f tu POM true a of report (CH C. Nevertheless, it constitutes a breakthrough which opened the way to this new new this to way the opened which breakthrough a constitutes it Nevertheless, C. 2 11 , entry entry , n VO . H an 4,4,4,16 3 (Reprinted fromWu (Reprinted - ) )( IL 40 ( le of characterization of of characterization of le ion [W ion + n (CH ]

, (B) Images of th of Images (B) , cation fo sml polyoxotungstates: simple from s - hshnu sl o te idvs iooyxain [W isopolyoxoanion, Lindqvist the of salt phosphonium C + ) 8 H 2 CH cations. 17 Comment citer cedocument: 6 O and lacunaryandKeggin ) 3 2 This 19 N) O) ] ([Eu(XW 2) 2 3 m article - [PO , with , 11 102] [101, . H

) - et al. et e N 4 IL was published published was IL is

[WO(O POM +

protected Unfortunately ) trihexyl(tetradecyl) or tributyl(hexadecyl) phosphonium phosphonium tributyl(hexadecyl) or trihexyl(tetradecyl) , [98] 11 et al et 3 . hy highlight They a with O ) hc dos o . P. a 120 at Pa.s 0.5 to drops which s) [PW

- with the permission from the Royal Society of Chemistry.) of Society Royal fromthe permission the with IL POM 39 2 , )

) by at room temperature temperature room at 2 [103] synthesized another POM another synthesized 2 12 ] - m ] n ye O ( POM type - - copyright. 4 O - type POMs ([XW POMs type IL + ] , X ,

40 n modified POMs by conveniently exchanging conveniently by POMs modified . look

wt Ehqa 18/25 Ethoquad with ] (A) DTA and and DTA (A) , 15, = =

Si, B, n B, Si, s All phosphotungstic acid acid phosphotungstic

by ed ie yloih syrup yellowish a like rights this this

Bourlinos the fact that the long alkyl chain chain alkyl long the that fact the e Fgr 13 Figure see in a ratio 1/2. It displays a high high a displays It 1/2. ratio a in T reserved. g =

at conducti in the glass phase glass the in 13, 15). Even if they are solid solid are they if Even 15). 13, 11 s m

- O - at RT. RT. at ethyl 35 encapsulat 39 t al et

] - n °C), obtained from the the from obtained °C), IL using aliquat 336 as as 336 aliquat using IL vity - , X, - tri b ) . – -

Later, . eprtr pos of plots temperature = [100] n

n 2004. in H odciiy and conductivity - C Te thermal The °C. 6 P, Si, B, n B, Si, P, octylammonium ed O 3 - - ((CH [PW

48 like substance substance like 10.1002/ejic.201900990 19 and and

h resulting The lse SEC cluster ]

Dietz Dietz 2 °C - 12

3 at at (Table )(C [99] O

95 for the the for 40

18 = t al et and ]

They °C H 7, 8,7, 37

26 2

in ) . , .

O Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde °C. - 2 122 11

as theoxidant. Oso hs study this of POMs VO soitd ih active with associated [75] N 12

the good activity photocatalytic d for

- O °C

oeyiiaoim eoougtt [ peroxotungstate dodecylimidazolium 40 In 2013, Li and coworkers and Li 2013, In on but unfortunately but on 40 - ] 2000 chain (see Figure 2) and the anionic part was Keggin heteropolyacid heteropolyacid Keggin was part anionic the and 2) Figure (see chain 2000 ). T ] 4 2 - [110] g , -

anion ) the POM the [104] r blw 100 below are

- oee, hn ope to coupled when However, (3 s’ tried

They were a were They -

sulfonic group)propyl 3 group)propyl sulfonic field . 12 with lacunary Keggin lacunary with [106]

Comment citer cedocument: O to synt to oeaae used xometalates - IL possess IL , 40

. This

- the most commonly encounter commonly most the ] - The mdzlu [mimC imidazolium From then and during and then From 4 methyl

be used as a reaction induced phase induced reaction a as used be article - peroxo peroxo and [BW and

hetize analogue compound ( compound analogue hetize n

°C - it was it ll liquid at room temperature (T temperature room at liquid ll h dfnto, epciey 45 n 9. °C 95.5 and 94.5 respectively definition, the oxidative esterification was successfully catalyzed by this this by catalyzed successfully was esterification oxidative octylammonium (TOA octylammonium 5 [BW is -

bten 25 (between es 3 protected - - - also

octylimidazolium nos {PO anions octyl IL where the cations were two butylimidazolium linked butylimidazoliumwereIL two cations the where 12 a phase transition from a cryst a from transition phase a a 12 O O solid with a melting point above the 100 the above point melting a with solid egradingrhodamine B. 40 T 82.6 °C and its decomposition temperature reaches temperature decomposition its and °C 82.6 as catalysts for the epoxidation of olefins. One of of One olefins. of epoxidation the for catalysts as used 40 - g by ] and (TOA) and ] 3

] - - and the critical gelation concentrations, that the the that concentrations, gelation critical the and 5 type POMs are more efficient gelators than the the than gelators efficient more are POMs type methyl imidazolium ( imidazolium methyl - copyright. ed - methylimidazolium halides IL. They developed IL. They halides methylimidazolium ) two new POM new two ) aaim usiue Kgi heteropo Keggin substituted vanadium cationic surfactants cationic

n - ] HC 45 POM a 4 4

[Mo [MO(O this work on liquid crystals, a very close close very a crystals, liquid on work this

2 °C All im 8 (table ) . rights + O ] [107] 4 ) cation associated with Keggin with associated cation ) 2 - [GeW 26 ed cations ar cations ed [W IL with an imidazolium imidazolium an with IL 2 I 2009 In . ) mimPS (n ]

2 reserved. The polyoxomolybdate The ] 2 4 O } - 12

11 3− ILs were reported, with phase phase with reported, were ILs

able 2 d = O ) reve ])

Lindqvist Lindqvist (M=W, Mo) for oxidative oxidative for Mo) (M=W, 40 - ) entries mimPS 10 and 12) with melting melting with 12) and 10 separation catalyst, which which catalyst, separation 3 , [(C ] respectively at 0 at respectively ] [P

2 Qiao al phase to an isotropic an to phase al , entry 14 entry , W e n

H a imidazolium 12

e t b li be to led 2 , see Figure 2 Figure see ,

O 7 n t al et +1 - 40 POM 11). It has been been has It 11). ) ] 3

N(CH 10.1002/ejic.201900990 as catalyst for for catalyst as . - . [108] [105] 16) and very very and 16)

[Mo

°C - bearing

With t With based IL based hy all They 3 s, which s, report )]

quid at at quid lyanion lyanion

°C and °C 6 (mp + O )). -

type type (n 19 [109] ] ed ed 27 he

2 = = a –

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde W attributed °C 17 -

vanadium substituted POM substituted vanadium phase at about 82.4 about at phase and 80% relative humidity) relative 80% and of them of VO eedn o te hmcl opsto o te heteropolyanions. the of composition chemical the on depending ate below 100 below ate 4 5

- [PMo [SiMo Meanwhile, there is clearly a structure effect on the physicochemical properties: as properties: physicochemical the on effect structure a clearly is there Meanwhile, usiue htrplain ([PW heteropolyanion substituted 62 - ] -

containing one under the same conditions. conditions. same the under one containing 7 ILs exhibit higher thermal stability and conductivity than their ammonium ammonium their than conductivity and stability thermal higher exhibit ILs to - . hn soitd ih (1 with associated When ). 11 enter enter an increase in the migration of ions in the compound. In parallel they run the the run they parallel In compound. the in ions of migration the in increase an 11 VO VO 11 rature - O usiue htrpl anions. heteropoly substituted 40 40 39 easily in the POM the in easily ad (mimPS) and ]

] and (mimPS) and ] M(H °C Comment citer cedocument: - dependent behavior with a phase transition from the gel state to the the to state gel the from transition phase a with behavior dependent . (Table .

This °C 2 O)] . This material exhibits higher conductivity (8.60*10 conductivity higher exhibits material This . article n monium salts. monium -

- 2 is C Tbe , nre 2 entries 2, (Table °C oxidizability greater exhibited atoms Mo contained that IL than that of its solid analogue and displays the advantages advantages the displays and analogue solid its of that than y - M Fe = (M

state protected

entries s whic , there is a significant improvement in the conductivity, the in improvement significant a is there , 7 [SiW 3 [PW - ILs’ family (T family ILs’ electrolyte h increases with temperature. This phenomenon can phenomenon This temperature. with increases h -

no [ anion by 2 9 11 3 V - copyright. III 9 -

- (3 MoO 3 V 2 L n fud applicati found and IL Cu , O 5 - 3 sulfopropyl)pyridinium cation, the phase phase the cation, sulfopropyl)pyridinium 40 ). Their electrochemical performance varies varies performance electrochemical Their ). O [111] ], 40  40 . [110]

II ] - All ta wr vr vsos t room at viscous very were that ] exhibit a gel state at room temperature temperature room at state gel a exhibit 6 SiW

Mn , [115] - h POM The [PW , tungstates with the [PW the with tungstates rights able

They extend They In addition, more vanadium atoms atoms vanadium more addition, In

6 11 - II POM analogue synthetized O reserved.

29 Co , 2 2 39 O 11

) entries ] . 2 VO [98] 8

- - and co and and their performances were were performancestheir and

ILs II

40 n is rniin metal transition its and Cr , hs eis f POM of series This ] ed 4

(mimPS) - 3 [PMo , -

0 ons for depollution, depollution, for ons III workers their studies to three three to studies their - Ni , 3 6 s xetd t expected, As 39 ePMI gels POM/IL se ). - Phosphonium 10.1002/ejic.201900990 II 11 5 12 4 [SiW ) with long long with ) . VO 0 [117 O ther various various ther ). - 2 40 [116]

- 40 S ] 122] 11 3 . ] – cm 4 VO [112

anion

Most They - - - and - 1 ILs ILs 40 114]

28 he at at ], - - .

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde

11 O

List of real POM Listreal of 39 M(H (C ( (( ((n (( (TOA) (TOA) (DODA) (DODA) (DODA) (DODA) (DODA) (( (( (( (C (Me( ( POM ((CH H n n n n n 8 5 C ------H mim) C C C C C C 12 n 5 14 14 10 8 12 8 - 2

i 3 H H range the in IL - ( O)] m )(C 4 5 H H H H C n [GeW [BW 17 17 )

- 2 8 27 27 21 25 15 13 9 8 7 2 C [Mo H ) ) [BW [SiW [PW - 18 [W )( )( )( ) [Eu(BW [Eu(SiW 3 3 4 L b cagn te iiougtt t tasto metal transition to silicotungstate the changing by ILs 16 NCH 3 NCH 17 H - NCH n n n /5 12 H ) - - - 2 37 12 3 6 - O C C C O 11 - 11 33 N) O 11 ILs found in the literature in found the ILs )[(CH O (M 6 6 4 O 40 11 O ) 19 Comment citer cedocument: 3 3 O H H H 3 40 3 ) 3 ) ] ] 39 N) 39 [PO ] ) 3 3

39 13 13 9 ]

11 [PO 3 [PO ) ] 11 ]

This = [PO ] ) ) 3

3 O

3 3 P O 2 [PO 87 P P CH 4 Mn, Fe, Co, Ni, Cu, Zn) Cu, Ni, Co, Fe, Mn, + 39 39 [WO(O 4 4 + + ) . [WO(O 4 (MoO(O ) ) ) article 2 ) - (MoO(O 2 2 3 [W 2 4 2 2 Table °C. 108 ] [W [PW ] [WO(O O)

6 n 6 O O is H)((CH 12 2 19

) 2 19 O protected 2 ) ] 2 ] ] 2

2 ) 40 2 4 ]

) 2 ) ] 4 2 ) ] 2

] ) 4

]

4 ] 4 ] ] 2

CH by 1 2 - O) copyright. 5 3 m gather to tries ). Meanwhile, Cavaleiro Meanwhile, ). H)N

) obtained by Shakeela Shakeela by obtained 2 All H[ - rights PW 24.6 12 6,6, reserved. O

6,14 an exhaustive list of true POM true of list exhaustive an 40 °C ]

+ , [123] ) cations. ) 65 RT - (°C) range Melting 82.6 RT RT RT RT RT 75 0 32 27 34 37 42 - 65 55 35 48

6,6,6,14

------

IL IL IL IL IL IL

hl TOA while

) 4 t al et [PW et These compounds These al. . extended this extended . 10.1002/ejic.201900990 11 [124] O -

39 substituted substituted +

displayed Fe(H [101, [101, 102] [100] [100] [99] ref [107] [106] [105] [104] [104] [104] [75] [75] [103] [103] [103] [103] [103] [101, 102] [101, 102] at of salts

2 O)] 29

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde (PyPS) (PyPS) (mimPS) (mimPS) (mimPS) (mimPS) (C (C (( (( (( (( (( (TOA) (( (( (N,N,N’,N’ (N,N,N’,N’ (mimPS) (mimPS) (( (( (( (( (( (( (( (PyPS) (PyPS) n n n n n n n n n n n n n n 12 10 ------C C C C C C C C C C C C C C mim) mim) 6 14 14 14 10 14 14 14 7 8 7 6 6 7 H H H H H H H 8 H H H H H H H 7 4 4 6 [ [P [PMo [PW [PW 15 17 15 13 13 15 13  27 27 27 21 27 27 27 3 4 7 5 5 4 4 4 ) ) ) ) ) ) ) [PW [PMo [SiW [SiMo [SiW [PW - 2 [Mo [Mo )( )( )( )( )( )( )( 4 4 4 4 4 3 4 SiW W N N N N N ( N - - n n n n n n n n ( ( 11 9 + + + + + + n n 17 V ------11 ) ) ) ) ) ) VO C C C C C C C C 11 11 - - 8 8 8 6 5 5 5 8 VO 9 11 3 VO 11 C C O O 11 [ [ [ [ [ [ 4 4 4 4 4 4 4 14 V O MoO VO 11 Comment citer cedocument:       H H H H H H H VO O 8 6 VO 26 26 H 3 40 40 H H VO ------9 9 9 9 9 9 9 62 O 39 40 ] ] SiW SiW SiW SiW SiW SiW 29 ) ) ) ) ) ) ) ] ] 17 13 40

This 3 3 3 3 3 3 3 ]

40 40 ] ] 40 )N P P P N N P N

) ) ]

40 40 ] ] 4 4

+ + + + ] + + +

- - ] ]

) ) ) ) 11 11 11 11 11 11 + ) ) ) N’’,N’’ N’’,N’’

article 8 8 5 6 ) 5 5 6 [PW [P [SiW [PW O O O O O O [SiW [SiW [PW 8 [ 39 39 39 39 39 39  2 W Fe(H Fe(H Fe(H ] ] Cu(H -

SiW 10 9 9 is 11 16 V 11 11 V V

- - VO V protected 3 (CH VO VO 3 CH 2 O O 2 2 2 O 2 11 2 O)] O)] O)] O 40 O)] 40 40 O 40 40 40 3 ] 62 3 ] ) ] ]

39 ) ] ]

2 ]

guanidinium)

] guanidinium) by copyright. 3 3 All [PW [PW rights 12 12 O O reserved. 40 40 ] ]

80 92 88 82 92 103 84 91 95 87 83 95.5 94.5 27 - 27 78 RT 70 68 RT 73 91 RT RT 61 50 50 95 59

------90

IL IL IL IL

- 40

10.1002/ejic.201900990 [113] [112] [112] [98] [98] [98] [98] [111] [111] [111] [109] [108] [108] [117, 118] [117, 118] [117, 118] [117, [117] [122] [120] 122] 120, [119, [119] [116] [116] [115] [115] [114] [114] [113] [113]

11 11 11 6 6 6 5 5 5 and cooling and [ [ [ [PW 39 39 39 39 39 39 [ [ O O O Comment citer cedocument:      Zn(H Cu(H Ni(H Co(H Fe(H Mn(H ------39 39 39 SiW SiW SiW SiW SiW IL Mn(H Co(H Fe(H This 11 - of POM with H with POM of ILs ILs s O 2 2 2 2 2

O)] O)] 11 11 11 11 11 2 O)]

O)] O)] 39 catalysts and it is ext is it and catalysts article O)] °C 2 O O O O O 2 RhCH O)] 2 O)] O)]

39 39 39 39 39

Ni(H Mn(H Co(H Cu(H Cr(H

r nt o fe ue i ctltc reaction. catalytic in used often so not are , is

the catalyst often precipitate often catalyst the 2 protected CO 2 2 2 2 O)] O)] 2 O)] O)] O)] 2 H)]

2 by O [125] copyright. 2 . Especially for tungstic POMs with Lindqvist with POMs tungstic for Especially .

Fo ended to the solid salts IL salts solid the to ended r POMwithKeggin theW structure All rights A nother POM reserved. s

, which offers the properties the offers which , - point . ILs 40 40 40 40 40 RT - - - - 24 - - 73 40

25 24 70 70 70 34

------87 87 87 108 87 .6 87

- - - IL

material

0 0 0 to

be considered be - rmed and after after and rmed [97] POMs s 10.1002/ejic.201900990

is driven by by driven is hs at is part This

[124] [124] [124] [124] [124] [123] [123] [123] [117] [117] [117] [117] 118] [117, [78] [124] catalysts catalysts 6+

is the the is /W

31 5+

. 3 Alcohols oxidation [100]

. Representation of Representation . oxidation with hydrogen peroxide is the one of the most studied reaction without without reaction studied most the of one the is peroxide hydrogen with oxidation

2 ial,tedgaaino H of degradation the Finally, ) 2 [97] } 4

] are more inactive than molybdic or vanadic inactiveareanalogues more thanmolybdic redox

3 -

n [{WO(O and w vr atv seis ee eotd n characterized and reported were species active very Two Comment citer cedocument: potential, high catalytic performances are nevertheless reported. Thus, Thus, reported. nevertheless are performances catalytic high potential, peroxo complexes complexes peroxo This

2 O article

2 -

Os r reported. are POMs - omn hmgnos hss r mlin Atr cooling, After emulsion. or phases homogeneous forming 2 pot synthesis synthesis pot ) is 2

} protected     [{WO(O ] 2 2 by O - -

based ionic based se iue 13 Figure (see 2 copyright.

n O in a 2

) eaugtt ([W decatungstate 2 } 2 2 

All has to be considered mainly for safety safety for mainly considered be to has O et al et hy c a tase aet in agent transfer as act They 2 rights ] 2 liquids (N liquids -

. (a) and [PO and (a) [126] reserved. ) but many other species can be be can species other many but )

Furthermore,theydevelo - butylpyridinium bisulfate bisulfate butylpyridinium 4 10 {WO(O O . [97] 32 ]

4 - 2 based ) ) 2

} 4 10.1002/ejic.201900990 ] 3 -

(b) with the the (b) with IL catalytic - POM POM ped a a ped 32

s are selectivity after 6 hatselectivity 90 after6 species decreases. Therefore, a compromise leads to the best activity for for activity best the to leads compromise a Therefore, decreases. species and 92.7 and 17 10 ) The 2 – = O (CH 4 m ain n re t ajs te mhpii caatr f h ctls between catalyst the of character amphiphilic the adjust to order in cation um

ad 1 and ] precipitation in water upon treatment with H with treatment waterupon in precipitation easier tobe 32 0, 4, 8, 13) ( 13) 8, 4, 0, - hs sihl hge slciiy o bnadhd ta [C than benzaldehyde for selectivity higher slightly a has ] conversion and selectivity for alicy for selectivity and conversion 11 regulated phase transfer catalysts and decatungstate anion can react with H with react can anion decatungstate and catalysts transfer phase regulated 3 ) % VO 2

with hydrogen peroxide in 1.5 molar ratio molar 1.5 in hydrogenperoxide with N

respectively) for a similar conversion of 66 of conversion similar a for respectively) % ) - -

40 4 butyl bridged species [PW species bridged [PMo ifcl to difficult

] n te eetvt o 78.3 of selectivity the and 4 2 Comment citer cedocument: -

oxidized and alkylammonium with different alkyl chain lengths. As the length length the As lengths. chain alkyl differentwith alkylammonium and , 2 - see

This 3 Keggin , which works as works which 11 - ehlmdzlu bslae [C bisulfate methylimidazolium VO Figure 14 Figure article were fully characterized and the wettability was estimated by by estimated was wettability the and characterized fully were

40 °C

and the ] oxidize is , with60.6

with excellent recyclability aftercentrifugation. protected ye [PW type et al. et ) are composed of polyethylene glycol (PEG) glycol polyethylene of composed are ) 31 P NMR that the effective catalyst formed during the during formed catalyst effective the that NMR P conversion rise They . 4 O [127] by the active species of catalytic oxidation reaction. oxidation catalytic of species active the 8 solution containing H containing solution (O % ain (see Figure 14 Figure (see ain copyright. 12

studied a series of amphiphilic POM catalysts POM amphiphilic of series a studied

2 O conversion of benzyl alcohol to benzaldehyde benzaldehyde to conversion alcohol benzyl of ) 8 a b converted be can 40 ] % c 3 ] lic and benzylic alcohol is comparatively is alcohol benzylic and lic

- 3

. alcohol, the primary alcohols with long long with alcohols primary the alcohol, -

which All

ne te ae odtos secondary conditions same the Under s rights pecies reformed insoluble salts. The The salts. insoluble reformed pecies 2 s t al. et O

up to88% 2 . , which allowed for homogeneous homogeneous forallowed which , reserved. for

T 2 2 mim][HSO O he authors reported “an inverse inverse “an reported authors he % [128] 2 ms 2 O ). The catalyst was tested for for tested was catalyst The ).

decreases, the encapsulation the decreases, of benzylic alcohol at 80 at alcohol benzylic of 2

- 2 a soluble compound. With With compound. soluble a based aqueous oxidation oxidation aqueous based O hy oiid h phase the modified They . ne glycol (PEG) glycol ne 2 in

o leye with aldehyde to These catalysts called catalysts These 4 12 ) Tee IL These ]). 2 O - O n (n = 4, 8, 13) 13) 8, 4, = (n n 40 2 2

] mim] 3 o om active form to 10.1002/ejic.201900990 - .

4 [W - chain chain bridged bridged - POMs POMs 10

O 2

th °C O 32 33 in e ] 2

The conversion was based on alcohols; alcohols; on based was conversion The Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde

- 8 (C) and PIPA and (C) 8 3 . .

eut o te eetv oiain f loos o leye wt H with aldehydes to alcohols of oxidation selective the of Results [128]

- phenylethanol the conversion lessthan17%. is - PIPA Catalyst PIPA PIPA PIPA 86% of selectivity and a conversion of 71 of conversion a and selectivity of 86% kable enhancement of reaction rates with the employment of PIPA of employment the with rates reaction of enhancement kable - 13 (D). (Reprinted from Hao Hao from (Reprinted (D). 13 - - - - 13 8 4 0 Comment citer cedocument:

This - peroxotungstate article di n Conv. (%) Conv. - hnltao, ylhxnl dpeymtao, u fr n for but diphenylmethanol, cyclohexanol, phenylethanol, ain; otc age esrmns f PIPA of measurements angle Contact cations; is 96 91 88 71 . b

protected The selectivity was based was selectivity The

a by - et al. et copyright. ILs with phase transfer properties that can be be can that properties transfer phase with ILs Sel. (%) Sel. Indeed 86 84 79 82 [128]

- Ray diffraction pattern. Therefore, PIPA PIPA Therefore, pattern. diffraction Ray

with the permission from the Royal Society of Society Royal the from permission the with b All ,

f rights

or benzyl alcohol, benzaldehyde was was benzaldehyde alcohol, benzyl or

reserved. - 96% for for ee tms ihu any without times seven rm PIPA from

2 O 2

n ae oe various over water in - () PIPA (A), 0 - 10.1002/ejic.201900990 o PIPA to 0 - 13 was was 13 - (B), 4 - 13 34 -

with aselectivity up im] °C Epoxidation of olefin of Epoxidation - t al. et 3 , the conversion of cyclooctene in cyclooctene in cyclooctene of conversion the , . 2 of - [W Representation of the salts of the the of salts the of Representation methyl

separating homogeneous epoxidation catalysts fromseparating epoxidation homogeneous the products. 12 2 O im] [105] 11 - phase to emulsion, then emulsion, to phase - - ad N and ] 2 hexyl mdzlu prxtnsae [ peroxotungstate imidazolium [W

2 O eotd w poi (N protic two reported at theend ofat Comment citer cedocument: - 3 11

- to 99 ] was proved to be the most active catalyst among them for the the for them among catalyst active most the be to proved was ] This methyl - eyiiaoim eoougtt [HC peroxotungstate hexylimidazolium s article

% T

- his (seeFigure 15 mdzlu prxtnsae [C peroxotungstate imidazolium is et al. et

protected the reaction.” study provides study [105] to biphasic, and finally the catalyst self catalyst the finally and biphasic, to peroxotungstate peroxotungstate

by copyright. ). - IL “catalytic system switched the reaction reaction the switched system “catalytic IL 2

O C

2 12 an effective approach to circumvent the circumvent to approach effective an

- All as co as dodecylimidazolium dodecylimidazolium mim] rights - no [W anion oxide was obtained between 24 and 24 between obtained was oxide ay antation, the catalyst can be easily easily be can catalyst the antation, - s oxidant. After 4 h without solvent without h 4 After oxidant. 2 reserved.

[W an important role in the reaction. reaction. rolean inthe important 2 O 2 O 11 11 ) s catalyst as ]) 6 6 ] mim] 2 im] -

ih hi efcec for efficiency their with

2 [W 2 [W 2

peroxotungstate O 2 10.1002/ejic.201900990 O 11 - ) n two and ]) 11 precipitat s ad 1 and ]

f r the or ed 35 -

(CH

Catalyst (0.005 eq), substrates (1 eq), H eq), substrates eq), (1 Catalyst (0.005

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde t auos H aqueous wt%  

3 - ) like substance of of substance like ( Oxidative cleavage of olefin cleavageOxidative olefin of Desulfurization n - C 8

Substrates H one d 17 et al. et i rdsluiain HS mto remains method (HDS) drodesulfurization

m o {PO of ums ) the complete the h sm pbiain lo ecie ta te ecin of reaction the that described also publication same The

3 in oxidative cleavage of olefin. of cleavage oxidative in N] [104] 2 3

O {PO 2

Comment citer cedocument: otiig opud i t in compounds containing proposed a biphasic system with hydrogen peroxi hydrogen with system biphasic a proposed t 90 at 4 [WO(O [( This n

4 - sulfur removal of the system by using four highly viscous POM viscous highly four using bysystem the of removal sulfur

[MO(O C article °C 8 H , cyclohexene was was cyclohexene , 2 2 17 ) Products is O 2

) ] 2 protected 3 4

2 and alcohol N(CH (30 wt%,90 eq), (30 2 ad rmr achl i te ae odtos ed to lead conditions same the in alcohols primary and } ) 2 ] 4 (M }

3 by )]

- ammonium = ILs [100] oxidation carboxylic into acid

Mo or W) as catalyst for a model oil oil model a for catalyst as W) or Mo e D treatment. HDS he .

u i hexane in cut Yield (%) Yield °C All With 0.005 eq of POM of eq 0.005 With , 3h. , rights 80 67 72

reserved. in Russia Russia in an important challenge in fuel fuel in challenge important an at f {PO of salt

The results of this publication this of results The - 1,6 synthetized a yellowish a synthetized - ii wt 72 with dioic h rsls given results The ide 4 de and de as [WO(O

a . it was one of the the of one was it [100] - IL and 2 eq of eq 2 and IL 10.1002/ejic.201900990

N : 2

- ) methyl 2 ] 4 % } 3

yield and and -

N 36 in - -

pH=1, 10 mg/L RB, 0.2 g/L catalyst, under UV under g/Lcatalyst, mg/L10 0.2 RB, pH=1, n(H 8 [C [C Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde et al. et mim]   2

14 12

O mim] mim] 2 [(n )/n(DBT)=6, m(model oil)/m(POM )/n(DBT)=6, [(n [(n Catalyst Photoreaction Other organic reaction [(n , proposed a catalyst prepared by partial exchange of the protons of the [H the of protons the of exchange partial by prepared catalyst a proposed , 2 - [Mo - - C - C C 4 4 C [Mo [Mo 12 8 12 8 H - H H - H 00 chain 2000 IL photocatalyst was described by described was photocatalyst IL 6 17 25

25 O 8 8 ) O O ) ) 3 ) low 3 3 19 NCH 3 NCH 26 26 NCH NCH . ih mlig on a 82.6 at point melting a With ]. ] ]

POM melting points melting 3 3 3 ] 3 ] ] 3 ] 3 3 {PO 3 {PO {PO Comment citer cedocument: {PO - IL Rhodamine B (RB) B Rhodamine - - This 4

ucinlzd lyiiaoim chloride alkylimidazolium functionalized mdzlu ctos n a molybdo a and cations imidazolium 4 4 [MoO(O 4 [MoO(O [WO(O [WO(O . [106] article s

The POM The (acidic reaction): 80 77 1 2 2 2 st ) is 2 ) ) . 2 )

2 [108] 2 ] 2 protected ] - ] 4 ] 4 IL) 4 } 4 } } }

= The results for photocatalytic degradation of RB are RB of degradation photocatalytic for results The - - light for 90 min. 90 for light Sulfur Sulfur IL were measured via degrading the dye the degrading via measured ILwere 50, V(model oil)=5 mL, 2 V(model oil)=5 50,

(%) after three catalytic runs catalytic after three (%) - by ILs synthetized with n with synthetized ILs - copyright. ILs based on octamolybdate [ octamolybdate on based ILs removal(%) 100 100 100 100 Dong

a . All [104]

°C et al. et rights

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and used for acidic reaction forand used in 2011. in was

h,60 - idvs polyoxometalate: lindqvist

= stable.

% °C

a 39 [107] .

[108]

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- 48 presented a liquid liquid a presented 48 se Figure (see

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Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde

- IL (0.3 g), alcohol (17 mmol), acetic acid (34 mmol), 100 mmol), (34 acid mmol), acetic (17 alcohol g), IL(0.3 tive esterificationaldehyde of s

f t prn htrplai. oevr euso cue drn te reaction the during caused emulsion Moreover, heteropolyacid. parent its of Benzyl alcohol cyclohexanol s

Substrates 1 (Table 7 ethanol ethanol ethanol - octanol Comment citer cedocument:

This

, e ).

O ntry article 2 , the main product was benzoic acid and the yield of the ester ester the of yield the and acid benzoic was product main the , 3 is various other aldehydesvarious withmethanol. other )

. protected

2 O - 2 L aayt maintained catalyst IL by

(30 wt%) (30 Run copyright. 8 1 1 1 1 1

cyclohexanal, could also be converted to the to converted be also could cyclohexanal, All racteristic of the POM the of racteristic

°C drastically a rights . [106] , 6 h 6 , Conv. (%) Conv.

5 reserved. ; rformed with good esterification esterification good with rformed 91 94 37 89 55 90 ), while ), b

inofcatalyst. absence

affected the yie the affected

pivalaldehyde presented presented pivalaldehyde the - IL for the oxidative oxidative the for IL Yield (%) Yield

90 93 36 89 54 88 [106] xeln catalytic excellent

- IL catalyst. This catalyst. IL

10.1002/ejic.201900990

ld of methyl methyl of ld

and can be can and 38

- 2 Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde

- wt 2 Other Applications

H 2 O and M and pival benzaldehyde benzaldehyde benzaldehyde 2 cyclohexanal benzoic acid benzoic c , IL (0.1 g), aldehyde (1 mmol), 8 h, 8 mmol), 8 (1 aldehyde g), IL , (0.1

Substrates yield of benzoic acid. ofyieldbenzoic aldehyde itchell in Spain in itchell of

the oxidation of benzaldehyde, and after the H the after and benzaldehyde, of oxidation the -

ILs. By using [SiW using By ILs.

Comment citer cedocument: This

corrosion resistance against acetic acid vapors of copper metal metal copper of vapors acid acetic against resistance corrosion article Run ((

1 1 1 1 4 1 n

opened new avenues towards unexpected exciting practical exciting unexpected towards avenues new opened -

C is

6 protected H H 13

2 ih ul eeto o te cd rtcin properties. protection acid the of retention full with O ) 11 4 2 N

- (mmol) 4 4 4 4 4 4 O IL, after mechanical damage, the POM the damage, mechanical after IL, 0 by +

39 o (( or )

°C structure. However, a small proportion of the the of proportion small a However, structure. copyright. Cu(H ; b

ome groups, especially the teams the especially groups, ome

unless otherwise stated, yields of the corresponding yieldsofthe corresponding stated, unlessotherwise - 2 IL n CH O)] a - All . C - [106] based treatmentbased 3 7 rights OH (mL) OH 6 H -

4 4 4 0 4 4 - or [SiW or 15

eprtr POM temperature ) reserved. 4 N rinsing with organic solvents, organic with rinsing +

) , 11 2 Conv. (%) Conv. O te ad i coworkers his and Streb O 2 39 91.5

92 93 89 86 86 was used up, they were theywere up, used was . Fe(H [118]

2 - O)] se Fi (see ILs as coatings coatings as ILs Yield (%) Yield 10.1002/ejic.201900990 5 - 88.5

45 77 92 61 70 paired with paired - of Streb in Streb of IL coating IL 31 ue 16 gure

c NMR P

39 ). ).

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde focused their attention on the antimicrobial the on attention their focused - 17 - innocent role of the cations for such a property, a such for cations the of role innocent and ) hexyl, 4 . N

3 6 + P) ) . 6 . aureus S. . [ Cu disks (d=1 cm) exposed to aqueous acetic acid (50%) vapor for 24 h. a) coating: coating: a) h. 24 for vapor (50%) acid acetic aqueous to exposed cm) (d=1 disks Cu 3 10 121] [120,  , and particularly against against particularly and , [PMo - - SiW heptyl and heptyl ni 11 12 iley.) m ain can egh modified length chain cations um O

O hs suis revealed studies These - , which resulted from the increase of the positive electrical charge of of charge electrical positive the of increase the from resulted which , 39 Os ((MePh POMs 40 Cu(H he same year, Hu Hu year, same he

.nH (( Comment citer cedocument: n - octyl - 2 2 C This O)] O]) O]) 5 H b non b) ; article 11 - ammonium cations ammonium on ) 4 N

+ is atra Te eut idctd ht h aon o water of amount the that indicated results The bacteria. ) 6

3 [ protected P)  - - otd u ik c caig cmeca I [ IL commercial coating: c) disk; Cu coated 3 SiW [PMo 11 . aureus S. that by O 12 39 copyright. O Cu(H activity of POM of activity the 40 t al. et - .nH

ILs revealed to be useful for the protection the for useful be to revealed ILs exhibit

auay POM lacunary longer chains result chains longer O)] ed h atmcoil activity antimicrobial the All 2 . Moreover, the variation of the the of variation the Moreover, . ] played O])

. rights good antibacterial activities against activities antibacterial good [129] Rpitd from (Reprinted s

a reserved.

high activity against activity high - etd the tested the POMs and phosphonium phosphonium and POMs the ILs against clinically relevant relevant clinically against ILs

also [SiW ing Streb Streb 11 ky oe n the in role key a

in higher activity. higher in 39 et al. et efficiency ]

10.1002/ejic.201900990 8 indicat - C , Mitchell ,

ard with paired 6 [118] mim]Br; d) d) mim]Br; E. coli E.

ih the with ing the the ing , ((

40 E. P. of of n et et -

15 11 forming an acid formingan h eclet yrpoi slet poete o tetra of properties solvents hydrophobic excellent the ) 4

) MO N) 4 1 N by 7 8 [SiW + Acid : 39 ) 8 s ] [ ed to be a be to ed upporting n−  hanical and chemical treatment, proving if needed, that needed, if proving treatment, chemical and hanical 11 -

SiW (M O - an orso poeto o POM of protection corrosion rain 39 ] and POM and ]

= 11 - - E. coli, P. aeruginosa, S. aureus S. aeruginosa, P. coli, E. Mn, Fe, Co, Ni, Cu, and Zn) for the removal of Cd of removal the for Zn) and Cu, Ni, Co, Fe, Mn, O ILs for water treatment such as Shakeela and Rao and Shakeela as such treatment water for ILs st

39 ((n by coordination coordination by able, biocidal surface layer surfacebiocidal able, multifunctional material capable of removing of capable material multifunctional Comment citer cedocument:

ad (( and ] (Reprinted from Mitchell, Streb Streb Mitchell, from (Reprinted - This C - 7 IL 2 IL H article 15 )

n = 4 N) - is ((n C -

L, give ILs, protected 8 6 - [SiW H C 13 to the lacunary POM but also but POM lacunary the to 6 H ) 13 3 ( 11 ) n by 3 heritage O (C - s C copyright. 39

14 14 od surface good ] H

H on porous silica, th silica, porous on 29 . Moreover,POM . - L otd tn smls POM samples. stone coated IL 29 )N)

. )N (Figure 1 (Figure

) et al. et All 8 (Figure 1 (Figure [SiW + rights ) 8 [122] [  11 - s reserved.

O - SiW with the permission fromWiley.) permission the with

deec ad water and adherence by formation of POM of formation by 39 7 ]. RO: Romery RO: ]. ) 8 . - 11 ) n They demonstrated demonstrated They . O - These results prompt other prompt results These - cyamnu sls of salts octylammonium ILs are not removed even removedeven not ILsare 39 e resulting functionalized resulting e POM

organic pollutants (e.g., (e.g., pollutants organic ] efficiently heavy metal heavy efficiently

2+ [124] o fiinl protect efficiently to

and Pb and -

ILs can efficiently can ILs who

stone; BB: Belgian BB: stone; 10.1002/ejic.201900990

2+ - suggested L 1 IL -

repellency metal ions metal - - IL based based IL L (( ILs th

= at the at

((n

41 n to - -

- L spotd n oos silica. porous on supported ILs

- oxidation into carboxylic acids. carboxylic into oxidation h vlrzto o boas ad oe uhr lk D Gregorio De like authors some and biomass, of valorization the

to the rheological properties of ILs phases. Catalysis probably remains probably Catalysis ILs phases. of properties rheological the to Comment citer cedocument: - 4 ILs This im][ - bn cevg o lignin. of cleavage bond O article to develop to HSO , is [131, 132] [131, 4

] protected . In contact contact In . - based liquid crystals remains mainly of fundamental of mainly remains crystals liquid based

sustainable processes of valorization of biomass for biomass of valorization of processes sustainable

- ih n accurate an with while imidazolium based ILs have been proven to proven been have ILs based imidazolium while lecules. lecules. review was to highlight how we can design POM design can we how highlight to was review nd tomorrow’s challenges. In particular, POM particular, In challenges. tomorrow’s nd by copyright.

(Reprinted from Mitchell, Streb Streb Mitchell, from (Reprinted

supported ionic liquid phases (POM phases liquid ionic supported with [130] On another hand, some avenues towards towards avenues some hand, another On All

lignin and in and lignin

Besides, Rogers’ team published two published team Rogers’ Besides, rights [133] reserved.

hie f h PM n more and POM the of choice These heir side, POM side, heir

the examples pave the way way the pave examples presence of molecular of presence t al. et 5 10.1002/ejic.201900990 [PMo

- SILPs) based SILPs) - [122] ILs offer a a offer ILs 10

ih the with V t al. et

2 have O - ILs 40 42 In - - ]

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde - 02. INRA, CNRS, University o University CNRS, INRA, 02.

Comment citer cedocument:

resu This . Taken into account the relatively easy high scale synthesis of of synthesis scale high easy relatively the account into Taken . lting POM lting Fuior A. Mr. and Duguet M. Mr. Basset, S. Ms. article is

protected f Versailles and Institut Universitaire de France are also also are France de Universitaire Institut and Versailles f

- ILs, these allow these ILs, This work is supported by a public grant overseen overseen grant public a by supported is work This by copyright.

All rights

envisioning fantastic developments fantastic envisioning reserved. - Saclay, ANR Saclay, a st five years five st 10.1002/ejic.201900990 for their help help their for - 11 - IDEX

by 43 -

Martinetto, Y.,Pégot, B., Roch-Marchal, CottynBoitte, B.,Floquet, S.(Auteurde

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