Living coordinative chain-transfer polymerization of α-olefins, followed by chemical functionalization of a Zn(polymeryl)2 intermediate, provides entry to end-group functionalized poly(α-olefinates) (x-PAOs) that can serve as a new class of non-polar building block with tailorable occupied volumes. Application of these x-PAOs for the synthesis and self-assembly of sugar-polyolefin hybrid conjugates demonstrate the ability to manipulate the morphology of the ultra-thin film nanostructure through variation in occupied volume of the x-PAO domain.

Living coordinative chain-transfer polymerization of a-olefins,f ollowed by chemical functionalization of aZ n(polymeryl) 2 intermediate,p rovides entry to end-group functionalizedp oly(a-olefinates) (x-PAOs) that can serve as an ew class of non-polar building blockw ith tailorable occupied volumes.A pplication of these x-PAOsf or the synthesis and self-assembly of sugar-polyolefin hybrid conjugates demonstrate the ability to manipulate the morphology of the ultra-thin film nanostructure through variation in occupied volume of the x-PAO domain.The self-assembly of amphiphilic materials comprised of chemically linked polar and non-polar segments gives rise to avariety of nanostructures in solution and the solid state that are instrumental for aw ide range of existing and future technological applications.[1] As such, there has long been ac orollary interest in the development of new classes of molecular and macromolecular building blocks for amphiphilic systems that are amenable to programmed structural changes as ameans by which to exert control over the relative magnitudes of entropic and enthalpic contributions to the self-assembly process and thereby over the final nanostructure that is formed.[2] Within these considerations,one of the most important structural parameters to vary is the relative free volume occupied by the polar and non-polar domains of an amphiphile.F or example,i nt he case of surfactants, entropically favorable aggregation of non-polar tails within asolvent that is compatible with polar head groups produces micellar structures that can adopt av ariety of shapes as af unction of the surfactant packing parameter, N s ,w hich is defined by the volume of the non-polar tail, V c ,t he crosssectional area of the polar domain of the assembly, a,and the length of the non-polar chain, L c ,a ccording to N s = V c /aL c . [3] On alonger length scale,the chemical tethering of polar and non-polar macromolecular chains produces amphiphilic block copolymers (BCPs) in which the enthalpic (repulsive) interaction between immiscible block domains can now drive microphase separation within the bulk BCP material to generate periodic arrays with feature sizes on the nanometer length scale.[4] Which specific solid-state microphase-separated morphology is preferred for agiven BCP (for example, body-centered-cubic (BCC) spheres,h exagonally packed cylinders,abicontinuous gyroid phase,o ra lternating lamellae) is then dictated by the magnitude of the Flory-Huggins interaction parameter for the pair of block domains, c,t he relative block domain volume fractions, f,t he overall block copolymer degree of polymerization, N,a nd temperature, T. Finally,g iant surfactants are am ore recent new class of amphiphile that consist of one or more polymer chains that are tethered to af unctionalized nanoparticle or inorganic cluster.[5] Thes elf-assembly and phase behavior of giant surfactants in solution and the solid-state possess characteristic features of both small molecule surfactants and of BCPs, and once a...

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