Block Copolymer Supramolecular Assembly beyond Hydrogen Bonding

Abstract

Supramolecular assemblies of block copolymers (BSAs) with low molecular weight additives require preferential interactions between the additive and one of the blocks. So far, only hydrogen bonds (HB) were explored to obtain BSAs. We report on three novel BSAs of block copolymer PS-block-P4VP with commercially valuable additives of the EDOT family. Two of the additives ((3,4-ethylenedioxythiophene) (EDOT) and 3,4-(2,2-dimethylpropylenedioxy)thiophene (ProDOT)) form the BSAs based on interactions others than HB. The morphology and some properties of the BSAs were studied by means of AFM, FTIR, and spectroscopic ellipsometry. The BSAs reveal cylindrical morphology with periodicity of ∼30 nm. In thin films the orientation of the cylinders can be switched from perpendicular to parallel by annealing in vapors of a suitable solvent. Extraction with a selective solvent results in porous films with porosity of ∼15%. These non-HB BSAs were compared with the HB BSA of HMeDOT as well as HABA BSA reported recently. The nature of the non-HB interactions is briefly discussed.

Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains

“…Therein, a wide variety of additives ranging from amphiphilic molecules to mesogens incorporating chemical groups that mediate supramolecular interactions with polymer chains can be chosen. Several kinds of noncovalent interactions are useful for binding these additives to polymers, such as ionic interactions, metal coordination, hydrogen bonding, or their combinations 8, 9, 10, 11, 12. However, to the best of our knowledge, there have been no examples of using halogen bonding.…”

2,5‐Diamide‐Substituted Five‐Membered Heterocycles: Challenging Molecular Synthons

“…Five-membered heterocycles are key molecular components in polymeric or supramolecular assemblies for applications in material science [1][2][3][4][5][6][7][8][9] and they are also ubiquitous molecular scaffolds in medicinal chemistry. [10][11][12][13] Gaining synthetic access to a large variety of differently substituted heterocycles can afford a wider set of molecular modules, thus further expanding their use as core scaffolds for natural products or pharmaceutical compounds.…”

Nickel Network Derived from a Block Copolymer Template for MnO2 Electrodes as Dimensionally Stabilized Lithium‐Ion Battery Anodes

“…First introduced by Vukovic et al., this approach offers considerable advantages over previously described polymer template‐directed synthesis of metal foams . The most striking advantage is the refined way of simply tuning the morphology of the overall template, PS‐ b ‐P4VP, by varying the addition of x (ratio between PDP molecules and P4VP monomer units) of a low‐weight amphiphilic compound . After annealing of the polymer films (Figure a), the formation of an open network structure facilitates removal of the amphiphile.…”

“…[30] Themost striking advantage is the refined wayo fs imply tuning the morphology of the overall template,P S-b-P4VP,b yv arying the additiono fx (ratio between PDP molecules and P4VP monomer units) of al ow-weighta mphiphilicc ompound. [31][32][33] After annealingo ft he polymerf ilms (Figure 1a), the formation of an open network structure facilitates removal of the amphiphile.Byimmersing the complex in ethanol, aselective solvent for PDP,ahydrophilic surface suitable for direct processing of the polymer template is generated ( Figure 1b). Thus,e lectroless plating can be employed to backfill the porous polymer template with the desired metal (Figure1c), and subsequently,t he remaining polymer is removed by pyrolysis.…”