Supramolecular Polymers and Assemblies. Andreas Winter
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clarity). Representative (a) TEM, (b) AFM, and (c) Scanning electron microscopy (SEM) images of the vesicles formed by the star‐shaped polymers are also shown (n = 169). Source: Zhang et al. [69]. Figure reproduced with kind permission. © 2012 The Royal Chemical Society.Figure 2.16 Schematic representation of POM‐centered supramolecular polymers via a surface‐started RAFT polymerization. As shown by representative TEM images, the morphology of the self‐assembled nanostructure depended on the length of the PS chains. Source: Cao et al. [72]. Figure reproduced with kind permission. © 2016 The Royal Chemical Society.Figure 2.17 Schematic representation of the morphologies of pristine PS488‐b‐P4VP95 (a) and the nanocomposite with added H4SiW12O40 (b). Source: Zhang et al. [76]. Figure reproduced with kind permission. © 2016 Elsevier B.V. Figure 2.18 Schematic representation of the self‐assembly of the heteroditopic monomer 22 in a head‐to‐tail fashion. The concentration‐dependency of the self‐assembly process, as studied by 1H NMR spectroscopy, is also shown. Source: Schmuck [20]. © 2001 Elsevier B.V.Figure 2.19 Schematic representation of the different self‐assembly modes of zwitterion 23 dictated by the length of the alkyl chain. Source: Schmuck et al. [79]. © 2007 American Chemical Society.Figure 2.20 (a) Schematic representation of zwitterions 24 functionalized with amino‐acid residues. (b) Representative TEM image of a vesicle formed by the self‐assembly of 24a in DMSO (after staining with uranyl acetate). (c) Calculated structure of a membrane segment (the Me‐groups of the alanine moieties, essential for the vesicle formation are depicted in yellow); a view along the rows of stacked dimers showing the vesicle curvature as well as side view of the stacked dimers showing their alternating antiparallel orientation. Source: Rehm et al. [80]. Figure reproduced with kind permission. © 2008 American Chemical Society.Figure 2.21 Schematic representation of the tris‐zwitterion 25. The AFM images of the assemblies after spin‐coating onto mica substrates are also depicted: large plates were obtained on the surface at high rotational speed (7000 rpm, a and b); the plates merged at lower rotational speed (5000 rpm, c) and, finally, fully disintegrate into the 2D network of ribbons (d). A cross‐sectional plot of three representative plates is also shown (e, also depicted as yellow line in b) exhibited uniform heights and diameters of c. 450 and 2.5 nm, respectively. Source: Rehm et al. [82]. Figure reproduced with kind permission. © 2012 The Royal Chemical Society. Figure 2.22 Polarizing microscopy image of the PAA–dodecyltrimethylammonium complex (extension of λ = 1.5 nm). Source: Antonietti and Conrad [87]. Figure reproduced with kind permission. © 1994 Wiley‐VCH.Figure 2.23 Schematic representation of the supramolecular grafting of sulfonates onto P4VP. Source: Ikkala et al. [93].Figure 2.24 Schematic representation of the formation of helical strands from the achiral polyacetylene derivative 25 induced by ion pairing with chiral amines. Source: Yashima et al. [101]. © 1999 Springer Nature.Figure 2.25 (a) Schematic representation of polymers R‐28 and 29 that self‐assemble into right‐handed double helices in polar‐aprotic solvents. (b) Wide‐angle XRD pattern and AFM phase image (40 nm × 40 nm) of R‐28 × 29 along with a molecular model of the double‐stranded helical structure. Source: Maeda et al. [103]. Figure reproduced with kind permission. © 2008 American Chemical Society. Figure 2.26 Schematic representation of the two different structural modes for stoichiometric PECs. (a) Ladder‐type structure and (b) “Scrambled egg” structure.
3 Chapter 3Figure 3.1 Schematic representation of the various types of architectures accessible via H‐bonding interactions (A: H‐bonding acceptor, D: H‐bonding donor) [3]. Source: Redrawn from Binder and Zirbs [3]. © 2007 Springer Nature. Figure 3.2 (a) Classification of H‐bonds according to Jeffrey and Saenger (D: H‐bonding donor, A: H‐bonding acceptor, M: metal ion). Source: Jeffrey and Saenger [16]. © 1991 Springer Nature.Figure 3.3 Schematic representation of various single H‐bonding motifs.Figure 3.4 Schematic representation of various two‐centered H‐bonding motifs (A: adenine, T: thymine, G: guanine, C: cytosine).Figure 3.5 Schematic representation of various triple H‐bonding motifs (A: adenine, T: thymine, G: guanine, C: cytosine).Figure 3.6 Schematic representation of triple H‐bonding arrays exhibiting different Ka values (D: H‐bonding donor; A: H‐bonding acceptor, KA: association constant in CHCl3). Source: Brunsveld et al. [5].Figure 3.7 (a) Schematic representation of various quadruple H‐bonding motifs (from left to right). Source: Refs. [18,19] and Prabhakaran et al. [20]Figure 3.8 Schematic representation of Napy‐induced translation of homodimeric into heterodimeric assemblies via quadruple H‐bonding. Two examples according to Corbin and Zimmerman (a) and Chen (b) are shown in [21,37].Figure 3.9 Schematic representation of heterodimers based on sextuple H‐bonding systems. Source: (a) Chang and Hamilton [38] and (b) Yang et al. [41].Figure 3.10 The utilization of single H‐bonding for the formation of main‐chain supramolecular materials (left) and inter‐chain connection polymer blends (right). Source: Redrawn from Binder and Zirbs [3]. © 2007 Springer Nature.Figure 3.11 The formation of supramolecular ladder‐type polymers and networks based on monomers 1 and 2. Source: St.Pourcain and Griffin [73].Figure 3.12 Schematic representation of the formation of a supramolecular polymeric network using double H‐bonding interactions of the self‐complementary uradiazole units.Figure 3.13 (a) Schematic representation of the telechelic PDMSs 3 as monomers for the supramolecular ring‐chain equilibrium polymerization. (b) FT‐IR spectra of (3b)n at two different concentrations (c = 1.4 and 20 g l−1). (c) Concentration dependence of the reduced specific viscosity of (3b)n and the corresponding dibenzyl ester Bn–3b–Bn (Bn = benzyl, hexane, 25 °C). Source: Abed et al. [4]. Figure reproduced with kind permission. © 2000 American Chemical Society.Figure 3.14 (a) Schematic representation of the chiral two‐centered H‐bonding unit 4 with its bicyclo[3.3.1]nonane core. (b) Schematic representation of the structure‐dependent supramolecular self‐assembly of monomers 5 and 6.Figure 3.15 (a) Schematic representation of the supramolecular polymer (7)n. (b) Schematic representation of the dense 1D packing of 7a in a slipped fashion (the red twisted blocks represent the PBI core, the bay substituents are shown in gray cones with a blue apex and H‐bonding interactions are indicated as green lines). Source: Würthner et al. [101]. Figure reproduced with kind permission. © 2016 American Chemical Society. Figure 3.16 Schematic representation of the formation of parent DPP from its N‐t‐Boc‐protected derivative 8; DPP self‐assembles into linear supramolecular polymer due to double H‐bonding interactions. Figure 3.17 (a) Schematic representation of the N‐t‐Boc‐protected DPP oligomers 9 and 10. (b) Schematic representation of the N‐t‐Boc‐protected DPP and PBI dyes 11 and 12. Figure 3.18 Schematic representation of the supramolecular polymerization of the homotelechelic monomers 13a and 13b into an alternating copolymer. Source: Fouquey et al. [2].Figure 3.19 Schematic representation of the LC supramolecular polymer14. Source: Kotera et al. [115].Figure 3.20 (a) Schematic representation of the formation of supramolecular gels based on triple H‐bonding motifs in concert with additional non‐covalent interchain interactions. Representative field‐emission scanning electron microscopy (FE‐SEM) images of the fibers obtained from the dried benzene gels are also shown (left: 15a, right: 15b). (b) Schematic representation of monomer 16 used for the supramolecular polymerization with N‐dodecyl