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60%, and 100%, respectively). Source: (a) Yan et al. [59]. © 2011 John Wiley and Sons, (b) Yan et al. [59]. Figure reproduced with kind permission; © 2012 Wiley‐VCH.Figure 11.12 Schematic representation of the supramolecular gel formed by the cross‐linking of metallocages via crown ether recognition. The material exhibited a multi‐stimuli‐responsive behavior (e.g. switchability between a gel‐like and liquid state). Source: Lu et al. [60]. Figure reproduced with kind permission; © 2018 American Chemical Society.Figure 11.13 Schematic representation of the formation of the 1 : 1 complex
16@CB[6] and its metallo‐supramolecular polymerization into linear chains or a 2D polymer networks when Cu(II) or Ag(I) ions, respectively, are added. Source: Whang et al. [62]. © 1996 American Chemical Society.Figure 11.14 Schematic representation of the two‐step assembly of
16–
17 with CB[6] and Cd(II) ions into a double‐chained supramolecular 1D polymer. Source: Redrawn from Park et al. [63].Figure 11.15 Schematic representation of the typ ligands
18–20, as monomers, for the two‐step supramolecular polymerization: (a) homometallic polymer, based on homotrimeric host–guest complexes, and (b) heterobimetallic polymer, based on heterotrimeric host–guest complexes. Source: (a) Liu et al. [70]. © 2013 The Royal Chemical Society, (b) Joseph et al. [71]. © 2014 American Chemical Society.Figure 11.16 Schematic representation of supramolecular triblock copolymer
21. Source: Yang et al. [73]. © 2010 American Chemical Society.Figure 11.17 Schematic representation of the formation of 1D‐stacks from
22 by synergistical H‐bonding interactions. Source: Nieuwenhuizen et al. [75]. © 2010 John Wiley and Sons.Figure 11.18 Schematic representation of homoditopic polymer
23. The AFM imaging revealed fiber formation as a result from substituents in 6‐position (scale bar: 100 nm). Source: Appel et al. [76]. Figure reproduced with kind permission; © 2011 American Chemical Society.Figure 11.19 Schematic representation of polymers
24–26 and their self‐assembly behavior. Source: Mes et al. [79]. © 2011 American Chemical Society.Figure 11.20 Schematic representation of the supramolecular architecture
27. Source: Shao et al. [81]. © 2004 American Chemical Society.Figure 11.21 Schematic representation of monomers
28 and
29 as well as their self‐assembly into a linear supramolecular polymer; the SEM image of a fiber grown from (
28⋅⋅⋅
29)
n is also shown. Source: Li et al. [85]. Figure reproduced with kind permission; © 2011 The Royal Chemical Society.Figure 11.22 Schematic representation of the self‐assembly of
30 and
31 into a pseudorotaxane network. Source: Li et al. [87]. © 2011 The Royal Chemical Society.Figure 11.23 (a) Schematic representation of the self‐assembly of a star‐shaped molecule
32 into a helical columnar triplex; (b) schematic representation of the fabrication of an ordered array of columnar lines on a mica substrate. Source: van Hameren et al. [88]. © 2008 American Chemical Society.Figure 11.24 (a) Schematic representation of OPE
33 and (b) its concentration‐dependent self‐assembly into nanoparticles, microspheres or giant fibrillar structures. Source: Ajayaghosh et al. [90]. © 2006 John Wiley and Sons.Figure 11.25 Schematic representation of the two‐step, self‐assembly of
34 and
35 into a supramolecular superlattice; the polarizing optical microscope (POM) image is also shown (
34‐to‐
35 ratio of 8 : 1, 100 °C). Source: Fitié et al. [92]. © 2008 American Chemical Society.Figure 11.26 Schematic representation of the self‐assembly of
36 into supramolecular polymers and grafted polymers (in the absence and presence of
37, respectively). Representative TEM images of the spherical micelles and 1D fibers, obtained from the coassembly of
36 with
37a and
37b, respectively, are also shown. Source: Jamadar and Das [94]. © 2020 The Royal Chemical Society.Figure 11.27 Schematic representation of the hierarchical self‐assembly of the sulfonamide‐functionalized oligopeptide
38. Source: Teng et al. [96]. © 2019 John Wiley and Sons.Figure 11.28 Schematic representation of the supramolecular polymerization of
39 and
40 due to orthogonal host–guest complexation. Source: Wang et al. [98]. © 2008 American Chemical Society.Figure 11.29 Schematic representation of the polypseudorotaxane formation via an orthogonal three‐component self‐assembly process. Source: Wang et al. [103]. © 2009 The Royal Chemical Society.Figure 11.30 Schematic representation of the self‐assembly of a polycationic dendron with naphthalene dicarboxylic acids into cylindrical and spherical aggregates. Source: Redrawn from Gröhn et al. [104]. © 2019 John Wiley and Sons.Figure 11.31 Schematic representation of the pair of oppositely charged porphyrins (
412− and
424+/5+); a representative TEM image of the resultant nanotubes is also shown (inset: a tube trapped in a vertical orientation by a thick mat of tubes). Source: Wang et al. [109]. Figure reproduced with kind permission; © 2004 American Chemical Society.Figure 11.32 Schematic representation of the oppositely charged PBI (
43) and phthalocyanine dyes (
44), which gave a supramolecular helically stacked superstructure. Source: Guan et al. [110]. © 2005 John Wiley and Sons.Figure 11.33 Schematic representation of the proposed model of the two‐step, self‐assembly of the carboxy‐functionalized NBI
45 and the tetra‐cationic guanidiniocarbonyl pyrrole
46. Source: Samanta et al. [113]. © 2005 John Wiley and Sons.Figure 11.34 Schematic representation of the functionalized monomers
47 and
48. (a) Schematic representation of the supramolecular polymer formed by
47, CB[8], and
48 in a directional two‐step assembly approach. (b) The AF4 elution curve of the supramolecular polymer (water, as eluent, UV detector). Source: Song et al. [114]. © 2014 The Royal Chemical Society.Figure 11.35 Schematic representation of the heteroditopic monomers
49–51 used for the sequence‐controlled supramolecular copolymerization. Source: Hirao et al. [117]. © 2017 Springer Nature.Figure 11.36 Schematic representation of the formation of a supramolecular polymer due to CT interactions and pillar[5]arene‐based host–guest complexation. Source: Chen et al. [118]. © 2016 The Royal Chemical Society.Figure 11.37 (a) Schematic representation of the self‐assembly of the a myoglobin‐dimer and streptavidin with heme‐bis(biotin) conjugate
52; (b) AFM height image of the supramolecular polymer on a modified mica substrate (100 mM K
3PO
4 buffer, pH value of 7); (c) SEC traces (UV/vis absorption detector) of the supramolecular polymer (solid line) and the fragment obtained after cleavage of the disulfide bridges (dashed line). Source: Oohara et al. [24]. Figure reproduced with kind permission; © 2012 Wiley‐VCH.Figure 11.38 (a) Schematic representation of the formation of the supramolecular polymers (
53)
n, based on protein recognition. (b) SEC analysis of (
53)
n using reference proteins, as standards. Source: Kitagishi et al. [123]. © 2007 American Chemical Society.Figure 11.39 Schematic representation of the reversible switching between a thermodynamically and a kinetically stable architecture (linear polymer chain vs. spherical micelle). Source: Oohora et al. [124]. © 2017 The Royal Chemical Society.
12 Chapter 12Figure 12.1 Theoretical plot of the degree-of-polymerization (DP) vs. association constant (Ka in M−1) for a supramolecular polymerization (two different concentrations, isodesmic self‐assembly model). Source: Brunsveld et al. [2]. © 2001 American Chemical Society.Figure 12.2 Representative plots of the probability of binding (p) according to Weber [24] as a function of the total guest concentration ([G]0) and the Ka value (left axis) as well as the dissociation constant (Kd, right axis) at three different host concentrations [(a)–(c): [H]0 = 10−3 M, 10−5 M, and 10−7 M]. The thick horizontal bar indicates where [H]0 is equal to Kd and Ka−1. The contour lines represent 0.1 units of p (the p range from 0.2 to 0.8 is shaded gray. Source: Thordarson [20]. © 2011 Royal Society of Chemistry.Figure 12.3 Simulated binding isotherms (1 : 1 complexation, Ka = 100 M−1) for [H]0 = 10−6 M (red curve) and 10−5 M (blue curve); a random error of 2% was included in the simulation. Source: Thordarson [20]. © 2011 Royal Society of Chemistry.Figure 12.4 (a) SEC traces of [1]n and polystyrene references (eluent: CHCl3); (b) SEC traces of 2 and {[Ru(2)](BF4)2}n (eluent: DMAc, containing 5.5
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