Two- and Three-Dimensional Smectic Ordering of Single-Handed Helical Polymers(6)

Two- and Three-Dimensional Smectic Ordering of Single-Handed Helical Polymers

ARTICLESFigure3.Structuresofhelicalpoly-L-1’s.(A)WAXDpatternofanorientedpoly-L-1(-)filmpreparedfromaconcentratedLCbenzenesolution(ca.15wt%).Thereflectionswereindexedwithahexagonallattice;a)26.78Åandc)13.05Å,suggestinga15unitsper4turns(15/4)helicalstructure.(BandC)Optimized15/4helicalstructuresofpoly-L-1(-)(B,158-mer)andpoly-L-1(+)(C,58-mer)onthebasisofWAXDstructuralanalysesfollowedbymolecularmechanicscalculations(seeSupportingInformation).Eachstructureisrepresentedbyspace-fillingmodels,andfoursetsofhydrogen-bondedhelicalarrays(nandn+4)ofthependantsareshownindifferentcolorsforclarity.(DandE)Thedetailedstructureofpoly-L-1(-)(11-mer)takenfrom(B)isalsoshownbyastickmodelinD(sideview)andE(topview).Inthesemodels(B-E),thependantdecylestergroupsofpoly-L-1’sarereplacedbythemethylgroupsforclarity.(FandG)AFMphaseimagesofpoly-L-1(-)(F)andpoly-L-1(+)(G)onHOPG(scale)10×20nm).Schematicrepresentationsoftheleft-handedhelicalpoly-L-1(-)andright-handedhelicalpoly-L-1(+)structureswithperiodicobliquestripes(pinkandbluelines,respectively)whichdenoteaone-handedhelicalarrayofthependants,arealsoshown(right).Onthebasisofanevaluationofca.100molecules,thenumber-averagemolecularlength(Ln)andthelengthdistribution(Lw/Ln)were

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