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1 Eltroni Supplmntary Matrial (ESI) for Physial Chmistry Chmial Physis. This journal is th Ownr Soitis 2015 Eltroni Supporting Information Dviation of Polarity from Linarity in Liquid Mixturs Containing an Ioni Liquid Vijay Bniwal, Shashi Kant Shukla and Anil Kumar* Physial and Matrials Chmistry Division, CSIR-ational Chmial Laoratory, Homi Bhaha Road, Pun , India *Author for orrspondn: Tl: Contnts: 1. Sours, purifiation mthods and final puritis of sustans usd in th study 2. Struturs of th ioni liquids and solvatohromi dys usd in th study 3. Synthsis and purifiation of ioni liquids 4. Charatrization and purity of ioni liquids 5. Calulation of E T and othr solvatohromi paramtr 6. Sampl Prparation 7. Dtrmination of max for Rihardt s dy with th hlp of UV-vis sptrophotomtr 8. Rfrns

2 1. Sours, purifiation mthods and final puritis of sustans usd in th study: 1-Mthylimidazol with 99 % purity, n-utylromid with 99% purity, sodium diyanamid with 98 % purity and 2,6-diphnyl-4-(2,4,6-triphnyl-pyridinium-1-yl)phnolat ( 90%) wr purhasd from M/s Sigma Aldrih. 1-Mthylimidazol and n-utylromid wr distilld prior to thir us. Sodium ttrafluoroorat (98%) is usd as otaind from Mrk. Mthanol with 99.7% purity, formamid with 99.5% purity and DMSO with 99.5% purity wr usd as purhasd from Mrk. Milli-Q watr with th spifi ondutan of 5.5 x 10-6 Sm -1 was usd throughout th xprimnts.

3 Tal S1: Sour of ompounds, th purifiation mthods applid and final puritis of th ompounds usd in th study. Compound Sour Purifiation Mthods inal Purity 1-mthylimidazol M/s Sigma Aldrih Distillation >99.7% n-utylromid M/s Sigma Aldrih Distillation >99.7% Rihardt s M/s Sigma Aldrih Usd as is >90% E T (30) dy Sodium M/s Mrk Ltd. Usd as is >98% ttrafluoroorat Sodium M/s Sigma Aldrih Usd as is >98% diyanamid Mthanol M/s Mrk Ltd. Usd as is >99.7% DMSO M/s Mrk Ltd. Usd as is >99.5% ormamid M/s Mrk Ltd. Usd as is >99.5% Watr Milli-Q watr With spifi ondutan of 5.5x10-6 Sm -1 [C 4 C 1 im][b 4 ] Synthsisd in th laoratory Exss salts wr rmovd y filtration through Buknr funnl with lit powdr. Watr and DCM was rmovd y high vauum C. Purity >99% Halid ontnts < 25 ppm, watr ontnt < 50 ppm [C 4 C 1 im][(c) 2 ] Synthsisd in th laoratory Exss salts wr rmovd y filtration through Buknr funnl with lit powdr. Watr and DCM was rmovd y high vauum C. Purity >99% Halid ontnts < 30 ppm, watr ontnt < 50 ppm

4 2. Struturs of th ioni liquids and solvatohromi dys usd in th study H 3 C C 4 H 9 H 3 C C 4 H 9 B C C a H 2 O 2 O 2 O d igur S1. Struturs of (a) [C 4 C 1 im][b 4 ], () [C 4 C 1 im][(c) 2 ], () Rihardt s E T (30) dy, (d) Dithylnitroanilin dy and () itroanilin dy.

5 3. Synthsis and purifiation of ioni liquids Synthsis of ioni liquid was arrid out aording to th standard produrs dsrid in th litratur. irst [C 4 C 1 im]br ioni liquid was synthsizd y th quartrnization ration of 1-mthylimidazol and n-utyl romid. 1,2 or this 1-mthylimidazol and n-utyl romid wr mixd in 1:1.2 molar ratio and hatd undr rflux ondnsr for 15 h at 60 C, in inrt atmosphr undr nitrogn gas. Exss of n-utyl romid was rmovd y th xtration pross using thyl atat. Th ioni liquid was thn drid thoroughly undr high vauum for 6 h at 70 C. Synthsis of [C 4 C 1 im][b 4 ] and [C 4 C 1 im][(c) 2 ] wr arrid out y th anion xhang ration of [C 4 C 1 im]br. 3 [C 4 C 1 im]br was dissolvd in dihloromthan and thn sodium salt ontaining th rsptiv salt was mixd (1.2 molar ratio to that of [C 4 C 1 im]br). Th ration mixtur was allowd to stir for 24 h at room tmpratur in inrt atmosphr undr nitrogn gas. Exss of salts war rmovd y multipl filtration using Buknr funnl, dihloromthan was usd as th solvnt and lit was usd to aptur th xss salts. Th dihloromthan was rmovd y rota-vapour at 50 C. Thraftr, th ioni liquids wr allowd to dry undr high vauum for 6-10 h at 70 C.

6 4. Charatrization and purity of ioni liquids Charatrization of ioni liquids was don using th 1 H MR, 13 C MR and 19 MR thniqus. In ordr to hk th dissoiation of ioni liquid in watr mixturs th MR sptra wr also rordd of th mixtur of [C 4 C 1 im][b 4 ] with mthanol and watr. Th sptra for 1 HMR wr rordd at 200 MHz MR sptromtr from Brukr India Pvt. Ltd. whras, th 13 C and 19 MR sptra wr rordd at 500 MHz MR sptromtr from Brukr India Pvt. Ltd. All th MR sptra wr takn in th nat stat (no dutratd solvnt was addd to th sampls), using CDCl 3 apillary as antilok. Th MR sptra otaind for th ioni liquids in its pur stat and in th trnary mixtur ar givn in igur S2. Th watr ontnt of th ioni liquids was masurd using oulomtr and was found to lss than 50 ppm. Th halid ontnts of ioni liquid wr masurd using th standard Volhard titration mthod and wr found to lss than 25 ppm for [C 4 C 1 im][b 4 ] and lss that 30 ppm for [C 4 C 1 im][(c) 2 ]. 4 As it an assumd that th sodium mtal will xist in th form of its salt with romid ion, its xptd amount prsnt in th sampls is lss than 30 ppm.

7 (a) 1 H MR sptrum of pur [C 4 C 1 im][b 4 ] in nat ondition at 200 MHz using CDCl 3 apillary: g d a f () 13 C MR sptrum of pur [C 4 C 1 im][b 4 ] in nat ondition at 500 MHz using CDCl 3 apillary: g d a f

8 () 19 MR sptrum of pur [C 4 C 1 im][b 4 ] in nat ondition at 500 MHz using CDCl 3 apillary: B (d) 1 H MR sptrum of th mixtur of [C 4 C 1 im][b 4 ], watr and mthanol in nat ondition at 200 MHz using CDCl 3 apillary: f h d a g O H H O H

9 () 13 C MR of th mixtur of [C 4 C 1 im][b 4 ] with watr and mthanol: g d a f O H (f) 19 MR of th mixtur of [C 4 C 1 im][b 4 ] with watr and mthanol: B

10 (g) 1 H MR sptrum of pur [C 4 C 1 im][(c) 2 ] in nat ondition at 200 MHz using CDCl 3 apillary g d a f (h) 13 C MR sptrum of pur [C 4 C 1 im][(c) 2 ] in nat ondition at 200 MHz using CDCl 3 apillary f h a d g C C igur S2: 1 H, 13 C and 19 MR sptra (a-h) of pur ioni liquids and mixtur of [C 4 C 1 im][b 4 ] with mthanol and watr in nat onditions using CDCl 3 apillary as anti loking solvnt.

11 5. Calulation of solvatohromi paramtrs E T paramtr: Th E T valus for a givn solvnts is dfind as th normalizd valu of E T (30) paramtr using watr (E T = 1) and TMS (E T = 0) as rfrn solvnts. E T = [E T (30) solvnt E T (30) TMS ]/[E T (30) watr E T (30) TMS ] = [E T (solvnt) 30.7]/32.4 (1) E T (30) valu for a givn solvnt an alulatd from th molar transition nrgy (in kal mol -1 ) of th Rihardt s dy no. 30 (igur S1 ), at TP, (298 K tmpratur and 1 ar prssur), using quation (2). 5,6 E T (30) = h () max A = () max (2) * paramtr: This paramtr is a masur of dipolarity/polarizaility of solvnts and is alulatd y th solvatohromi shifts of th max valus of,-dithyl-4-nitroanilin dy (igur S1 d) using quation (3). 6 ν(d) max = π* (3) paramtr: Th valu of solvnts is otaind y using E T (30) and * paramtrs of th solvnts as shown y quation (4) 6 α = E T (30) π* (4) paramtr: Th hydrogn ond aptor asiity or paramtr of solvnts is dtrmind y quation (5) using th sptrosopi shift of 4-nitroanilin (igur S1 ) with rspt to,-dithyl-4- nitroanilin (igur S1 d). 6

12 ν() max = 1.035ν(d) max - 2.8β (5) 6. Sampl Prparation Sampl prparations wr arrid out undr th inrt atmosphr of nitrogn gas in glov ox. irst a stok solution of Rihardt s dy was prpard in DCM. Th stok solution thus prpard was addd drop wis to th ioni liquids. Aftr th addition of stok solution, DCM was rmovd from th ioni liquid with th hlp of high vauum at 50 C. Th inary mixturs of ioni liquids wr prpard y th addition of appropriat amount of th molular solvnt or psudo-solvnt to th ioni liquid in th glov ox. or th mixturs not ontaining ioni liquids, prparation of stok solutions wr not ndd and dy was dirtly introdud into th solvnts. Th inary mixtur ontaining th pro moluls was thn transfrrd to th uvtt for th masurmnt of max. All this produrs wr prformd in th inrt atmosphr of glov ox undr th nitrogn gas. Aftr introduing th sampls into th uvtt th max valus wr otaind with th hlp of UV-visil sptrophotomtr. Tmpratur of th sampl was kpt onstant at K using th Pltir stup with an auray of 0.01 K. All th inary mixturs wr prpard on mol fration asis.

13 7. Dtrmination of max for Rihardt s dy with th hlp of UV-vis sptrophotomtr Th wavlngth of maximum asorption ( max ) was dtrmind y using th Cary-50 UV-vis sptrophotomtr, with an auray of max 1 nm. Th rprsntativ sptra otaind for mthanol is shown in th igur S3. igur S3: A rprsntativ UV-vis sptra otaind for mthanol. or omparison, plots of rportd and masurd E T (30) valus ar shown for watr-dmso and mthanol-dmso inary mixturs in igur S4. 64 Rportd data Our data 55 Rportd data Our data E T (30) 56 E T (30) (a) 45 () x DMSO x DMSO igur SI 4: Comparison of th data with arlir rportd data for (a) watr-dmso and () mthanol-dmso mixturs.

14 8. Rfrns 1 P. Bonhot, A. P. Dias,. Papagorgiou, K. Kalyanasundaram, M. Gratzl, Inorg. Chm., 1996, 35, W. E. Gardinir, G. A. Bakr, S.. Bakr,. V. Bright, Maromoluls, 2005, 38, S.. Bakr, E. B. Brauns, T. M. MClsky, A. K. Burrlla, G. A. Bakr Chm. Commun,. 2006, A. Stark, P. Bhrnd, O. Braun, A. Mullr, J. Rank, B. Ondrushka, B. Jastorff, Grn Chm., 2008, 10, C. Rihardt, Chm. Rv., 1994, 94, C. Rihardt, Grn Chm., 2005, 7, 339.