Supramolecular Polymers and Assemblies. Andreas Winter
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tape‐like and cyclic rosette‐like shapes.Figure 3.22 Schematic representation of the supramolecular polymer 17 based on triple H‐bonding interactions, supported by π-π stacking hydrophobic interactions and a PBI core. A representative TEM image of the mesoscopic superstructures that were fabricated by evaporation of a methylcyclohexane solutions of 17 (c = 5 × 10−5 mol l−1) on a carbon‐Formvar‐coated nickel grid (200 mesh) and subsequent staining with uranyl acetate is also shown. Source: Würthner et al. [130]. Figure reproduced with kind permission; © 1999 Wiley‐VCH.Figure 3.23 (a) Schematic representation of the heteroditopic PBI 18. (b) Schematic representation of the supramolecular polymerization of 18 into cylindrical nanostructures. (c) Representative TEM image of the nanocylinders. Source: Sinks et al. [133]. Figure reproduced with kind permission. © 2005 American Chemical Society. Figure 3.24 (a) Scanning tunnelling microscopy (STM) image of the honeycomb structure on a Ag‐layered Si substrate (inset: high‐resolution view of the substrate surface) [134]. (b) STM image of the Lu@C82‐loaded network on the Au(111) surface (area of 55 × 40 nm2). Source: Silly et al. [135]. Figure reproduced with kind permission; © 2003 Nature Publishing Group and 2008 The Royal Chemical Society.Figure 3.25 Schematic representation of the stepwise fabrication of a hybrid structure starting from a supramolecular honeycomb PBI–melamine network. Source: Silien et al. [139]. Figure reproduced with kind permission; © 2009 Wiley‐VCH. Figure 3.26 Schematic representation of the supramolecular self‐assembly of 20a and 21 into ribbon‐like aggregates. Representatively, a field‐emission SEM image of the aggregates is also shown. Source: Yagai et al. [123]. Figure reproduced with kind permission. © 2007 American Chemical Society. Figure 3.27 Schematic representation of the monomers 22, which self‐assembled into toroids and linear fibrils (a) or, upon mixing, generated a supramolecular helical polymer (b). Source: Aratsu et al. [141]. Figure reproduced with kind permission. © 2020 Springer Nature.Figure 3.28 A chain‐extended supramolecular block‐copolymer based on triple H‐bonding arrays. PIB: poly(iso‐butylene), PEK: poly(etherketone). Source: Binder et al. [146]. Figure reproduced with kind permission. © 2005 Wiley‐VCH.Figure 3.29 Schematic representation of the homotelechelic PPOs23. The pictures show pure 23a, pure 23b, and an equimolar mixture of both (from left to right). Source: Cortese et al. [148]. Figure reproduced with kind permission. © 2012 American Chemical Society.Figure 3.30 Schematic representation of the reversible self‐assembly of the nucleobase‐functionalized oligo(phenylene‐ethynylene)s 24 (A: adenine, T: thymine). The optical micrograph of an annealed film of the polymer (24a···24b···)n at 130 °C is also shown (100× magnification, the inset shows a section with a 500× magnification). Source: Figure reproduced with kind permission; © 2003 The Royal Society of Chemistry. Figure 3.31 (a) Schematic representation of the bolaamphiphiles 25 (for the structures of adenine [A] and thymine [T], see Figure 3.30). (b–d) Energy‐filtered transmission electron microscopy (EF‐TEM) images of the fibers formed by self‐assembly in 10% ethanolic aqueous solution at 25 °C (b: 25a, c: 25c, d: 1 : 1 ratio of 25b and 25c; the scale bar represents always 1 μm). Source: Modified from Shimizu et al. [151]. Figure reproduced with kind permission. © 2001 American Chemical Society.Figure 3.32 A highly flexible material was formed via the self‐assembly of α,ω‐dinucleobase‐functionalized PTHF (e.g. 26a with two N4‐(4‐tert‐butylbenzoyl)‐cytosine moieties). Source: Modified from Sivakova et al. [152]. Figure reproduced with kind permission. © 2005 American Chemical Society.Figure 3.33 Schematic representation of two important self‐complementary quadruple H‐bonding arrays with high Ka values. Figure 3.34 (a) Schematic representation of the UPy‐functionalized homotelechelic monomers27. (b) Representation of the critical concentrations of 20 in supramolecular ring‐chain equilibrium polymerizations. Source: ten Cate and Sijbesma [11]. Figure reproduced with kind permission. © 2003 Wiley‐VCH.Figure 3.35 Schematic representation of the UPy‐functionalized homotelechelic monomers 29–31.Figure 3.36 Images of a bis‐UPy‐functionalized poly(ɛ‐caprolactam) that was processed into different scaffolds: (a) thin films, (b) fibers, (c) meshes (a representative SEM image is depicted), and (d) grids. Source: Dankers et al. [165]. Figure reproduced with kind permission. © 2005 Nature Publishing Group. Figure 3.37 Schematic representation of the fabrication of vascular graft from UPy‐equipped macromolecular components. The pictures show the results of the in‐vivo cell‐adhesion experiments. Source: van Alme et al. [166]. Figure reproduced with kind permission. © 2016 Wiley‐VCH.Figure 3.38(a) Schematic representation of the H‐bonded dimer 32. (b) SEM image of the surface roughness (scale bar: 2 μm). (c) Representation of the superhydrophobicity of the resulting surface: Water contact angle of c. 150°. Source: Han et al. [175]. Figure reproduced with kind permission. © 2004 American Chemical Society.Figure 3.39 Schematic representation of the formation of supramolecular AB‐type diblock copolymers due to complementary H‐bonding interactions. Source: Feldman et al. [178]. © 2008 American Chemical Society.Figure 3.40 Schematic representation of the UPy‐ and Napy‐functionalized homopolymers33 and 34. The microscopy images show the microstructure of the blends after annealing at various temperatures. Source: Modified from [178]. Figure reproduced with kind permission. © 2008 American Chemical Society.Figure 3.41 Schematic representation of the supramolecular diblock copolymers35 and 36. A representative TEM image of 35 showing the microphase separation in the solid state is also shown. Source: Rao et al. [186]. Figure reproduced with kind permission. © 2012 The Royal Chemical Society.Figure 3.42 Schematic representation of the formation of a strictly alternating supramolecular copolymer using the non‐self‐complementary monomers37 and 38. Source: Based on Park and Zimmerman [187]. © 2006 American Chemical Society.Figure 3.43 Schematic representation of the heteroditopic H‐bonding units 39–41.Figure 3.44 Schematic representation of the photoreversible formation of the supramolecular polymer (c‐42)n.Figure 3.45 (a) Schematic representation of the various bis‐UPy‐functionalized π‐conjugated chromophores43–45. (b) Schematic representation of the proposed energy‐transfer process within the supramolecular copolymers. (c) Representation of the emission colors of the three individual homopolymers and the three‐component copolymer in solution (top) as well as in the solid state (bottom). Source: Abbel et al. [195]. Figure reproduced with kind permission. © 2009 American Chemical Society.Figure 3.46 Schematic representation of the quadruple H‐bonding arrays 46 and 47 based on self‐complementary 1,3,5‐triamino‐2,4,6‐triazine derivatives (R denotes aliphatic and oligo(ethylene glycol) chains – chiral and non‐chiral ones).Figure 3.47 (a, b) Schematic representation of the self‐assembly of the heterodifunctional H‐bonding array48 into a supramolecular polymer. (c) Temperature‐dependent UV/vis absorption spectra of 48 (0.10 mM in decaline); the inset shows the evolution of the absorbance at 349 nm when the temperature was changed. Source: Ikeda et al. [197]. Figure reproduced with kind permission. © 2005 Wiley‐VCH.Figure 3.48 (a) Schematic representation of the linear supramolecular polymer49. (b) Representative electron‐microscopy images of the extended, densely packed fiber networks obtained from the solution of 49 (2.5 mmol l−1 in CHCl3/heptane, 1 : 4 ratio). Source: Berl et al. [198]. Figure reproduced with kind permission. © 2002 Wiley‐VCH.Figure 3.49 Schematic representation of the formation of homopolymers and diblock copolymers equipped with Hamiltonian receptors or barbiturate units. PS: polystyrene, PMMA: poly(methyl methacrylate), PLMA: poly(lauryl methacrylate), PnBuA: poly(n‐butyl acrylate). These macromonomers were assembled into supramolecular pseudo‐block copolymers via sextuple H‐bonding interactions. Source: Chen et al. [201]. Figure reproduced with kind permission. © 2012 The Royal Chemical Society. Figure 3.50 Schematic representation of the formation of a supramolecular helix–helix diblock copolymer. Source: Croom et al. [204]. Figure reproduced with kind permission. © 2016 American Chemical Society.Figure