2004 American Chemical Society.Figure 5.41 Schematic representation of the supramolecular polymers derived from 35 and 36. A representative SEM image of the fiber‐like assemblies also shown. The polymers could be disassembled in the presence of competitive guest molecules or anions. Source: Park et al. [110]. Figure reproduced by kind permission; © 2011 National Academy of Science.Figure 5.42 Schematic representation of the supramolecular 2 : 1 complex formed by γ‐CD and C60 in water. Source: Based on Andersson et al. [114].Figure 5.43 Schematic representation of a molecular tweezers on the basis of a bis‐calix[5]arene (38) and its encapsulation of a C60 guest in the cavity. Source: Based on Haino et al. [116].Figure 5.44 Schematic representation of the bis‐exTTF‐based molecular tweezers39 and its solvent‐dependent interaction with C60. Source: Pérez et al. [118], © American Chemical Society.Figure 5.45 Schematic representation of the heteroditopic monomer40 and of the corresponding supramolecular CT polymer (40)n. The AFM images of (40)n deposited onto a mica surface are also shown (left: 2D image, 277 nm × 277 nm; right: 3D image, 80 × 65 nm). Source: Fernández et al. [119], Figure reproduced with kind permission; © 2008 Wiley‐VCH.Figure 5.46 Schematic representation of the preorganized exTTF‐based receptor 41 and the analogous AB‐type monomer 42. The MALDI‐TOF mass spectrum of (42)n is also depicted. Source: Isla et al. [120], © 2014 John Wiley and Sons.Figure 5.47 Schematic representation of the formation of a supramolecular hyperbranched polymer starting from an AB2‐type monomer. Source: Fernández et al. [121], © 2008 American Chemical Society.6 Chapter 6Figure 6.1 Schematic representation of important crown ether hosts.Figure 6.2 Schematic representation of the (pseudo)rotaxane formation. Source: Zheng et al. [9], 2012 Royal Society of Chemistry.Figure 6.3 (a) Schematic representation of the AB‐type monomer 4 and the ball‐stick representation of the solid structure of the dimer (4)2 (counter ions were omitted for clarity). (b) MALDI time‐of‐flight mass spectrum of 4. Source: Cantrill et al. [35], © 2001 American Chemical Society.Figure 6.4 (a) Schematic representation of monomer 5. (b): Space‐filling representation of the [c2]daisy chain (5)2 (counterions were omitted for clarity). Source: Ashton et al. [38], © 1998 John Wiley and Sons.Figure 6.5 (a) Schematic representation of the self‐assembly of 6 into a polypseudorotaxane. (b) Schematic representation of the multifunctional monomer 7.Figure 6.6 (a) Schematic representation of the formation of a supramolecular polymer gel via the self‐assembly of a flexible AB‐type monomer. (b) Pictures of the supramolecular gel and its stimuli‐triggered gel–sol transitions (by changing either the temperature or pH value). Source: Dong et al. [41]. Figure reproduced with kind permission; © 2011 Wiley‐VCH.Figure 6.7 Schematic representation of the photoinduced supramolecular polymerization of 8 which was accompanied by sol–gel transition of the solution at high monomer concentrations. Source: Zheng et al. [43]. Figure reproduced with kind permission; © 2018 Elsevier B.V.Figure 6.8 Schematic representation of the self‐assembly of the complementary homoditopic monomers 9 and 10 (a) as well as 11 and 12 (b); the counterions were omitted for clarity [47]. Source: Figure reproduced with kind permission; © 2003 American Chemical Society.Figure 6.9 Schematic representation of polypseudorotaxane formation via selective crown ether recognition. Source: Wang et al. [49], © 2009 Royal Society of Chemistry.Figure 6.10 Schematic representation of the supramolecular self‐assembly of 15 and 12 (m = 10). The supramolecular polymer exhibited AIE‐based fluorescence in solution as well as in the solid state, i.e. in the electrospun nanofibers. Two representative SEM images (a/b) an a fluorescence microscopy image (c) of the fibers are shown. Source: Chen et al. [50], © 2015 The Royal Chemical Society.Figure 6.11 Schematic representation of the multifunctional monomer 16 and its transformation into a linear supramolecular polymer (poly‐16), covalent (co)polymers (17) and, eventually, covalent‐supramolecular polymers. A summary of the mechanical properties of these materials is also depicted. Source: Zhang et al. [51], © 2020 John Wiley and Sons.Figure 6.12 Schematic representation of the hetero‐tetratopic monomer 18, which gave a supramolecular polymer network due to a self‐cross‐linking process. Source: Wang et al. [52]. Figure reproduced with kind permission; © 2020 American Chemical Society.Figure 6.13 (a) Schematic representation of the formation of a host–guest assembly via threading MV2+ into the cavity of cryptand 19. (b) Schematic representation of the self‐assembly of AA‐type monomers with the BB‐type (MV2+)2‐monomer into linear supramolecular polymers. Source: Niu et al. [57], © 2011 American Chemical Society.Figure 6.14 Schematic representation of the formation of a cryptand‐based linear supramolecular polymer via three different reaction pathways. Source: Wei et al. [60].Figure 6.15 (a) Schematic representation of the unsymmetrical cryptand 20. (b) Schematic representation of the host–guest complex of 20 with the MV2+ and dibenzylammonium cation. (c) Schematic representation of the linear supramolecular polymer assembled from 20 and the ditopic guests 12 and 14. Source: Yao et al. [61], © 2018 John Wiley and Sons.Figure 6.16 Schematic representation of macromolecular building blocks for host–guest complexation, based on crown ether recognition. Source: Zheng et al. [9], © 2012 Royal Society of Chemistry.Figure 6.17 (a) Schematic representation of the (a) polymer chain extension via crown ether recognition. Source: Based on Gibson et al. [63]Figure 6.18 Schematic representation of the heteroditopic macromonomers 21. The nanofibers, fabricated from the chain‐extended polymer (21)n by electrospinning, showed a multiple degradation behavior. The representative SEM images show the fibers before (c) and after the respective treatment with K+ (a), NEt3 (b), Cl− (d), and heat (e). Source: Chen et al. [123]. Figure reproduced with kind permission; © 2016 The Royal Chemical Society.Figure 6.19 Schematic representation of the self‐assembly of the AB2‐monomer 22 into a supramolecular hyperbranched polymer.Figure 6.20 Schematic representation of the formation of dendritic pseudorotaxanes via a convergent synthesis. Source: Gibson et al. [72], © 2002 American Chemical Society.Figure 6.21 Schematic representation of the formation of star‐shaped and graft polymers (a and b, respectively), based on crown ether recognition. Source: (a) Zheng et al. [9], © 2012 Royal Society of Chemistry; (b) Gibson et al. [75], © 2009 John Wiley and Sons.Figure 6.22 Schematic representation of the formation of dendrimers, based on crown ether recognition: (a) threading‐followed‐by‐stoppering and subsequent Wittig exchange. and (b) sliding methodology. Source: Elizarov et al. [80], © 2002 American Chemical Society.Figure 6.23 Schematic representation of the formation of a [2]rotaxane via a thermal azide to alkyne cycloaddition “click” reaction. Source: Ashton et al. [82], © 1996 John Wiley and Sons.Figure 6.24 (a) Schematic representation of the so‐called Wittig exchange – transformation of the “reactive” rotaxane I into the “inert” rotaxane III via intermediate II. Source: Rowan et al. [76], © 2000 American Chemical SocietyFigure 6.25 Schematic representation of the formation of a mechanically interlocked daisy chain using the Wittig exchange (a) and the “threading‐followed‐by‐swelling” methodology. Source: Rowan et al. [76], © 2000 American Chemical SocietyFigure 6.26 Schematic representation of a supramolecular muscle/shuttle, based on the pH‐switchable [c2]daisy chain (28)2. Source: Coutrot et al. [88], © 2008 American Chemical Society.Figure 6.27 Schematic representation of building block 23 and the derived poly([c2]daisy chain) that was utilized for expansion/contraction studies. Source: Clark et al. [93], © 2009 American Chemical Society.Figure 6.28 (a) Schematic representation of the synthesis of a poly[2]rotaxane via Sonogashira cross‐coupling polymerization. Source: Sasabe et al. [94]Figure 6.29 Schematic representation of the synthesis of dendritic [4]rotaxanes by “dynamic covalent chemistry” (DCC). Source: Leung et al. [99], © 2005 American Chemical Society.Figure 6.30 Schematic representation of main‐chain pseudorotaxane formation via two different synthetic strategies: Multiple threading of macrocycles onto a linear polymer chain (top) and polymerization of
