Supramolecular AB Diblock Copolymers

Abstract

Hydrogen‐bonded duplexes of incompatible polystyrene and poly(ethylene glycol) chains have been prepared that show microphase separation (see picture). Differential scanning calorimetric studies of the phase transitions for these copolymers show that they behave like typical covalently bonded diblock copolymers at temperatures below 170 °C.

Monte Carlo Simulations of Metallo‐Supramolecular Micelles

“…We will consider the equilibrium between 2:1 and 1:1 ligand-metal complexes formed on the micelle core surface and in the bulk ( Figure 1a) and study the effect of the association energy of metal-ligand complexes, aggregation number and coronablock length on the monomer density distribution and core-surface coverage. The obtained results provide insights on the molecular principles of self-assembly of metallosupramolecular micelles and unzippable micelles (involving reversible interactions between blocks [4][5][6][7][8][9][10][11][12] ) in general, which can help future experimental design of smart (metallo-)supramolecular materials with desired properties.…”

“…''Unzippable'' block copolymers with the blocks of different chemical nature connected to each other by means of other reversible interactions such as hydrogen bonding or inclusion complexes have also been reported in literature. [4][5][6][7][8][9][10][11][12] Due to the heterogeneous structure of their building blocks, metallo-supramolecular micelles exhibit unprecedented capabilities. [3,13] For example, electrochemical, photochemical, and redox properties associated with metal-ligand complexation [14] can be further exploited in metallo-supramolecular micelles to monitor and control material properties.…”

Multi‐Responsive Supramolecular Double Hydrophilic Diblock Copolymer Driven by Host‐Guest Inclusion Complexation between β‐Cyclodextrin and Adamantyl Moieties

“…[13,14] The schizophrenic micellization behavior of linear PNIPAM-b-PDEA diblock copolymers has already been reported. [8,9,15] Recently, various types of non-covalent interactions, such as hydrogen bonding interactions, [16][17][18][19][20][21][22][23][24][25][26] metal-ligand interactions [27][28][29][30][31][32][33][34] and host-guest recognition [35][36][37] have been employed to construct supramolecular block or graft copolymers. [38] In the context of supramolecular chemistry, the hierarchical self-assembly of this novel type of block copolymers possesses unique characteristics.…”

Design of Heterocomplementary H‐Bonding RAFT Agents – Towards the Generation of Supramolecular Star Polymers

“…Some of these motifs can self-assemble to form dimers, [7] while other systems are constituted of two complementary units, hence forming heterocomplexes. [6] Based on this concept, it is possible to prepare block copolymers -polystyrene-block-poly(ethylene glycol), [10] polyisobutylene-block-polyetherketone [11] or poly(n-butyl acrylate)-block-poly(benzyl methacrylate)- [12] and homopolymer stars [4] by replacing the covalent bonds linking respectively the blocks or the core and the arms by noncovalent bonds like hydrogen bonds. However, to the best of our knowledge, the preparation of supramolecular complex polymeric structures such as block copolymers or polymer stars from chain transfer agents (CTA) bearing Hbonding complementary associating units has not been reported so far.…”