Supramolecular Polymers and Assemblies. Andreas Winter

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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, K_a = 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 mM NH₄PF₆). Source: (a) Ogawa and Kobuke [35]. © 2000 John Wiley & Sons, (b) Meier et al. [32]. © 2006 American Chemical Society.Figure 12.5 Schematic representation of the synthesis of the poly(daisy chain) 3. The SEC traces of 3 and of the utilized monomer are also shown (eluent: DMF containing 0.2 M NH₄PF₆). Source: Fang et al. [42]. © 2009 American Chemical Society.Figure 12.6 (a) Schematic representation of the formation of the supramolecular polymers (4)_n. (b) Reduced viscosity of (4a)_n in CH₂Cl₂ (▲x025B2;) and CCl₄ (●x025CF;), the corresponding calculated curves are also shown (dashed and solid line, respectively). Source: Abed et al. [48]. © 2001 Elsevier.Figure 12.7 Schematic representation of the ring‐chain‐mediated polymerization of 5 and 6. The bilogrithmic viscosity–concentration plot allowed the determination of the cpc value. Source: Huang et al. [50]. © 2007 American Chemical Society.Figure 12.8 Schematic representation of the supramolecular polymerization of monomer 7 in the absence (a) and presence of the chain‐stopping agent 8 (b). Source: Lortie et al. [56]. © 2005 American Chemical Society.Figure 12.9 Schematic representation of the β‐cyclodextrin‐dimer (9) and the adamantyl‐dimer (10). The evolution of the M_n of the supramolecular polymer (9···10)_n as a function of the β‐CD‐dimer concentration (determined by VPO) is also shown. Source: Hasegawa et al. [62]. © 2005 American Chemical Society.Figure 12.10 (a) Schematic representation of the stepwise synthesis of a water‐soluble polyrotaxane. (b) Plot of the experimental M_w according to AUC as a function of the theoretical DP (DP_nom, the nonideal behavior at high DP values was attributed to accidental chain termination and fractionation upon purification. Source: From Michels [87]. © 2003 John Wiley & Sons.Figure 12.11 Comparison of the ¹H NMR spectra of the metallo‐supramolecular polymer 11 and the corresponding metal‐free ligand (both recorded in DMSO‐d₆). In the spectrum of 11, the signals assigned to the end groups are asterisked. Source: Brunsveld et al. [89]. © 2015 American Chemical Society.Figure 12.12 Schematic representation of the supramolecular polymerization of 12a. The concentration dependency of the diffusion coefficient (D) is also shown. Source: Haino et al. [92]. © 2012 John Wiley & Sons.Figure 12.13 (A) Schematic representation of the chain‐extended supramolecular polymer {[(13)Fe(13)](PF₆)₂}_n. (B) DOSY of {[(13)Fe(13)](PF₆)₂}_n in the absence (a) and presence of TFA (b). Source: Mansfeld et al. [97]. © 2013 The Royal Society of Chemistry.Figure 12.14 Analysis of a H‐bonded supramolecular polymer in the keto‐ and the enol‐form by ¹H DQ‐MAS NMR spectroscopy. Source: Schnell et al. [99]. © 2002 The Royal Chemical Society.Figure 12.15 Positive turbo ion spray time‐of‐flight MS of 14. Source: Miyauchi et al. [63]. © 2005 American Chemical Society.Figure 12.16 (a) Schematic representation of the self‐assembly of 15 and C₆₀ into a supramolecular polymer; (b) STM image of the polymer deposited onto a HOPG surface (the inset shows the corresponding line profile; (c) schematic representation of the polymer with structural parameters. Source: (a, c) Liu et al. [114]. © 2006 American Chemical Society, (b) Figure reproduced with kind permission; © 2006 American Chemical Society.Figure 12.17 (a, b) Schematic representation of the supramolecular polymer 16 and the proposed binding motif. (c) STM image of a monolayer of 16 at the liquid–graphite interface (self‐assembled from a 1,3,5‐trichlorobenzene solution, the scale bar is 4 nm). Source: (a, b) Ciesielski et al. [117]. Figure reproduced with kind permission; © 2009 John Wiley & Sons, (c). Ciesielski et al. [117]. © 2009 Wiley‐VCH.Figure 12.18 Schematic representation of the formation of loops within metallo‐supramolecular polymers. The corresponding UHV‐LT‐STM images are also depicted. Source: Li et al. [120]. © 2020 American Chemical Society.Figure 12.19 (a) Schematic representation of a metallo‐supramolecular Sierpiński hexagonal gasket. (b) Visualization of the assembly by UHV‐LT‐STM imaging. Source: Newkome et al. [121]. Figure reproduced with kind permission; © 2006 AAAS.Figure 12.20 (a) Schematic representation of two metallo‐supramolecular “spiderwebs.” (b) The corresponding UHV‐LT‐STM images are also depicted. Source: Wang et al. [122]. Figure reproduced with kind permission; © 2019 American Chemical Society.Figure 12.21 AFM images of spin‐coated solutions of 17 (a–c) and 18 (d) on mica substrates; for 17, various ligand‐to‐metal ratios were utilized (a: 0.6, b: 0.85, c: 0.98). Source: Schwarz et al. [126]. Figure reproduced with kind permission, © 2010 American Chemical Society.Figure 12.22 (a) Schematic representation of the experimental setup; (b) histogram of the bound rapture forces at a pulling velocity of 118 nm s⁻¹. Source: Kudera et al. [138]. © 2003 John Wiley & Sons.Figure 12.23 Schematic representation of the self‐assembly of 19 into a linear supramolecular polymer, based on two different types of noncovalent interactions; the cryo‐TEM images of {[Fe(19)₂]Cl₂}_n are also shown (a: no staining, b: negative staining with uranyl acetate). Source: Gröger et al. [143]. Figure reproduced with kind permission; © 2011 American Chemical Society.Figure 12.24 (a) Schematic representation of the formation of a “polynanocage”; (b and c) AFM and TEM image of the polynanocage. Source: (a) Fan et al. [149]. © 2012 American Chemical Society; (b, c) Fan et al. [149]. Figure reproduced with kind permission; © 2012 American Chemical Society.Figure 12.25 Schematic representation of the formation of a pseudorotaxane of high molar mass that could be processed into rod‐like fibers. Source: Wang et al. [152]. Figure reproduced with kind permission; © 2009 Royal Society of Chemistry.Figure 12.26 Schematic representation of supramolecular diblock copolymers, based on multiple H‐bonding interactions and their temperature‐dependent microphase‐separation behavior [the two different representations denote a polyisobutylene and a poly(ether ketone) constituent block, respectively]. Source: Binder and Zirbs [145]. © 2006 Springer.Figure 12.27 SAXS data for the metallo‐supramolecular polymer obtained from macroligand 20 with Zn(II) ions [SAXS curves at various 20 to Zn(II) ratios are shown]. Source: Burnworth et al. [13]. © 2011 Nature Publishing Group.Figure 12.28 Representation of the solid‐state structure of the β‐CD–PEG polypseudorotaxane, with the PEG chain reaching through four unit cells of β‐CD dimers. The H‐bonding interactions between pairs of head‐to‐head connected CDs are shown (view along the b‐axis, hydrogen atoms are omitted for clarity). Source: Udachin et al. [164]. © 2000 American Chemical Society.Figure 12.29 (a) Schematic representation of the supramolecular polymer formed by the polyassociation of the AB‐type monomer 21. (b) Two views of the 1D arrangement of (21)_n (only the hydrogen atoms involved in the C–H···π interactions are shown, all other hydrogen atoms were omitted for clarity). Source: Zhang et al. [169]. © 2011 John Wiley & Sons.Figure 12.30 The form factor (P) for two polymers whose chains follow self‐avoiding walk statistics and which have a R_g of 100 Å. The Guinier and intermediate regions can be clearly seen. For (a) the chains are perfectly monodisperse (Ð of 1.0) and for (b) the Ð value is large (i.e. M_w/M_n = 6.4). The dashed line (c) qualitatively indicates the effect of a persistence length (L) of c. 10 Å, giving a third region with a slope of −1. Source: Whittell et al. [173]. © 2013 John Wiley & Sons.Figure 12.31 (a) Schematic representation of the metallo‐supramolecular polymerization of 21 with various divalent metal ions [e.g. Co(II), Ni(II)]. (b) The Co(II)‐containing polymer showed an electrochemically driven switchability between the gel and sol states. Source: (a) Gasnier

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