DirectingtheViedmaRipeningofEthylenediammoniumSulfateusing“Tailor-made”ChiralAdditivesThiPhuongThaoNguyena,PuiShanMonicaCheunga,LioraWerberb,JacintheGagnona,ReajeanSivakumara,CameronLennoxa,AaronSossina,YitzhakMastai*bandLouisA.Cuccia*a

[a]DepartmentofChemistry&Biochemistry,ConcordiaUniversity,7141SherbrookeStreetWest,Montréal,Québec,H4B1R6,Canadae-mail:Louis.Cuccia@concordia.ca[b]Bar-IlanUniversity,DepartmentofChemistry,RamatGan,Israele-mail:Yitzhak.Mastai@biu.ac.il

SupplementaryinformationThechiralityofcrystalscanbedistinguishedthroughcircularpolarizationobservedalongtheopticaxis,wherethecolorchangeonrotatingtheanalyserisoppositeforenantiomorphiccrystals.In1861,Gladstonestated:1

The most prominent colors observed for ethylenediammonium sulfate (EDS) crystals whenobservedbetweencrossedpolarizersareamberandblue.Accordingly,ourgroupidentifiesthechiralityofEDSbyobservingablue-to-amber-to-clearoranamber-to-blue-to-cleartransitiononrotatingtheanalyzerclockwise.2Thecorrelationofourmethodwiththe‘naturalorder’oflightisillustratedforadextrorotatoryandlevorotatorycrystalinFigureESI-1a,b,d,&e.AnothermethodtodistinguishthechiralityofEDShasbeendescribedbyMatsumoto,Soaiandcoworkers,where,startingwithcrossedpolarizers,dextrorotatorycrystalsdecreasedinbrightnesswhilelevorotatorycrystalsincreasedinbrightness,withclockwiserotationoftheanalyzerby45°(FigureESI-1c&f).3

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2016

FigureESI-1a,b&c.ColortransitionsobservedforadextrorotatorycrystalofEDSusingpolarizedlightmicroscopy:(a)blue-to-amber-to-clearwhenrotatingtheanalyzerclockwise,(b)blue-to-violet-to-red-to-orange-to-clearwhenrotating the analyzer clockwise and (c) decreasing brightness when rotating the analyzer 45° clockwise (centerimage:crossedpolarizers,leftimage:45°counterclockwiseandrightimage:45°clockwise).d,e&f:ColortransitionsobservedforalevorotatorycrystalofEDSusingpolarizedlightmicroscopy(d)amber-to-blue-to-clearwhenrotatingtheanalyzerclockwise,(e)yellow-to-orange-to-violet-to-blue-to-clearwhenrotatingtheanalyzerclockwiseand(f) increasingbrightnesswhenrotatingtheanalyzer45°clockwise(center image:crossedpolarizers,leftimage:45°counterclockwiseandrightimage:45°clockwise).(Scalebar=1mm)

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Figure ESI-2. CD spectra of trans-1,2-diphenylethylenediamine in CHCl3 – Upper spectra: (i) (1R,2R)-1,2-diphenylethylenediamine(3.5mM)withnoEDS(solidline),(ii)(1R,2R)-1,2-diphenylethylenediamine(3mL,3.5mM)shakenwith300mgl-EDS(106µm-150µm)for1hr.andcentrifugedfor20min.(blacksquares)and(iii)(1R,2R)-1,2-diphenylethylenediamine(3mL,3.5mM)shakenwith300mgd-EDS(106µm-150µm)for1hr.andcentrifugedfor20min.(redsquares).Lowerspectra:(i)(1S,2S)-1,2-diphenylethylenediamine(3.5mM)withnoEDS(solidline),(ii) (1S,2S)-1,2-diphenylethylenediamine (3.5mM) shaken with 300mg l-EDS (106µm - 150µm) for 1 hr. andcentrifugedfor20min.(blacksquares)and(iii)(1S,2S)-1,2-diphenylethylenediamine(3mL,3.5mM)shakenwith300mgd-EDS(106µm-150µm)for1hr.andcentrifugedfor20min.(redsquares).References:

(1) J.H.Gladstone,J.Chem.Soc.,1861,13,254–270.(2) L.A.Cuccia,L.Koby,J.B.NingappaandM.Dakessian,J.Chem.Educ.,2005,82,1043–

1045.(3) A.Matsumoto,T.Ide,Y.Kaimori,S.FujiwaraandK.Soai,Chem.Lett.,2015,44,688–

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