We designed and synthesized high χ-low N-maltoheptaose-(triazolium+/N(SO2CF3)2–)-polyisoprene-(triazolium+/N(SO2CF3)2–)-maltoheptaose ABA triblock elastomers featuring triazolium+/N(SO2CF3)2– (TFSI–) counteranion ionic interfaces separating their constituting polymeric sub-blocks. Spin-coated and solvent-vapor-annealed (SVA) MH1.2k-(T+/TFSI–)-PI4.3k-(T+/TFSI–)-MH1.2k thin films demonstrate interface-induced… Click to show full abstract
We designed and synthesized high χ-low N-maltoheptaose-(triazolium+/N(SO2CF3)2–)-polyisoprene-(triazolium+/N(SO2CF3)2–)-maltoheptaose ABA triblock elastomers featuring triazolium+/N(SO2CF3)2– (TFSI–) counteranion ionic interfaces separating their constituting polymeric sub-blocks. Spin-coated and solvent-vapor-annealed (SVA) MH1.2k-(T+/TFSI–)-PI4.3k-(T+/TFSI–)-MH1.2k thin films demonstrate interface-induced charge cohesion through ca. 1 nm “thick” ionic nanochannels which facilitate the self-assembly of a perpendicularly aligned lamellar structure. Atomic force microscopy (AFM) and (grazing-incidence) small-angle X-ray scattering ((GI)SAXS) characterizations of MH1.2k-(T+/TFSI–)-PI4.3k-(T+/TFSI–)-MH1.2k and pristine triBCP analogous thin films revealed sub-10 nm block copolymer (BCP) self-assembly and unidirectionally aligned nanostructures developed over several μm2 areas. Solvated TFSI– counterions enhance the oligosaccharide sub-block packing during SVA. The overall BCP phase behavior was mapped through SAXS characterizations comparing di- vs triblock polymeric architectures, a middle PI sub-block with two different molecular masses, and TFSI– or I– counteranion effects. This work highlights the benefits of inducing single-point electrostatic interactions within chemical structures of block copolymers to master the long-range self-assembly of prescribed morphologies.
               
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