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4 Chapter 4Figure 4.1 Schematic representation of the general architectures of metal‐containing polymers. Source: Wild et al. [67]. © 2011 The Royal Chemical Society. Figure 4.2 Schematic representation of the three main types of metal‐to‐ligand interactions. (a) Coordinative bonding; (b) ionic bonding; and (c) arene π‐complexation. Source: Refs. [2,46,84].Figure 4.3 Schematic representation of the different general methods utilized for the synthesis of metal‐containing (co)polymers. Source: Refs. [2,61].Figure 4.4 (a) Schematic representation of metal complexes containing pyridine‐based ligands of increasing denticity. (b) The Irving–Williams series.Figure 4.5 Schematic representation of the coordination polymers 1–3 showing an increased stability in solution due to enhanced metal‐to‐ligand interactions.Figure 4.6 Schematic representation of the synthesis of the heterobimetallic coordination polymer 4.Figure 4.7 Illustration of the sonication‐induced decrease in the molar mass of 2 (1.5 mM in toluene): (a) Molar mass distribution of samples taken during sonication. (b) Evolution of the MW value over five cycles of sonication (1 hour) followed by equilibration (23 hours). Source: Paulusse and Sijbesma [94]. Figure reproduced with kind permission. © 2004 Wiley‐VCH. Figure 4.8 (a) Schematic representation of the synthesis of coordination polymer 5 via the coordination of 1,4‐benzenediisocyanide to the [Pt3(μ3‐CO)(μ‐dppm)3]2+ cluster (the counterions are omitted for clarity, L^L: dppm). A representation of the X‐ray single‐crystal structure of the precursor cluster is also shown (here, only the phenyl C‐atoms bonded to each P‐atom are shown for clarity). Source: Bradford et al. [111]. Figure reproduced with kind permission. © 1994 American chemical society.Figure 4.9 Schematic representation of the synthesis of the metallopolymer 7 with linear Pt4 clusters within the main chain.Figure 4.10 Schematic representation of the synthesis of coordination polymer 8 featuring A‐frame‐units within the backbone.Figure 4.11 Schematic representation of the synthesis of 9, as a polymer‐analogs to cisplatin.Figure 4.12 Schematic representation coordination polymers through the center of the porphyrin rings. (a) Shish‐Kebab‐type assembly, (b and c) assemblies based on AB‐type monomers.Figure 4.13 Schematic representation of Shish–Kebab‐type metallo‐supramolecular polymers 10 and 11 incorporating phthalocyanine.Figure 4.14 Schematic representation of the synthesis of the metalloporphyrin‐containing polymer12 via a Glaser‐type polyaddition (a) and of the metallo‐supramolecular 2D ladder‐shaped assembly featuring enhanced charge mobility (b). Source: Taylor and Anderson [123]. © 1999 American chemical society.Figure 4.15 Schematic representation of the synthesis of a zigzag‐shaped metallo‐supramolecular coordination polymer. Source: You and Würthner [129]. © 2004 American Chemical Society. Figure 4.16 Schematic representation of the self‐assembly of a 4‐pyridyl‐substituted porphyrin derivative with Zn(II) ions toward 14.Figure 4.17 Schematic representation of the linear Au(I)‐containing metallopolymers 15, which exhibited an odd–even effect with respect to the chain conformation.Figure 4.18 Schematic representation of various metallopolymers containing ditopic NHC‐type ligands. (a) Monodentate and (b) bidentate binding.Figure 4.19 Schematic representation of the synthesis of the rigid metallopolymers 19.Figure 4.20 Schematic representation of the synthesis of the flexible metallo‐supramolecular polymer 20.Figure 4.21 Schematic representation of the synthesis of metallopolymers 21 and 23 based on tetrahedral bis‐bidentate complexes (a) and a phosphine‐based ligand (b), respectively.Figure 4.22 Schematic representation of the chemical structure of the metallo‐supramolecular polymer 22, an illustration of the proposed helical 3D‐conformation is also shown. Source: Kaes et al. [175]. © 1998 Wiley‐VCH.Figure 4.23 Schematic representation of the metallopolymers 24 and 25. The picture shows the green color of 24a that could be changed reversibly to colorless upon electrochemical reduction of the Cu(II) centers. Source: Hossain et al. [181]. Figure reproduced with kind permission. © 2013 Wiley‐VCH.Figure 4.24 Schematic representation of the synthesis of coordination polymers 26 and 27 containing bridging [Ni(mnt)2]2− units.Figure 4.25 Generalized schematic representation of the self‐assembly of ditopic bis‐tridentate ligands and divalent transition metal ions into linear metallo‐supramolecular polymers. Source: Redrawn from Chiper et al. [52]. 2009 John Wiley & Sons.Figure 4.26 Schematic representation of the synthesis of metallopolymers bearing amido‐ or imido‐linkages via two different routes (denoted as methods III and Vb, respectively, see also Figure 4.3).Figure 4.27 Schematic representation of the synthesis of metallo‐supramolecular assemblies from a flexible bis‐terpyridine ligand and Ru(II) ions.Figure 4.28 Schematic representation of the Ru(II)‐containing chain‐extended polymer 31.Figure 4.29 Schematic representation of the general structure of a metallo‐supramolecular homo as well as a diblock copolymer. Source: Redrawn from Schubert et al. [186].Figure 4.30 Schematic representation of the synthesis of polymers equipped with designated metal‐binding sites via the end‐functionalization and the initiator route. Source: Hoogenboom and Schubert [233]. © 2006 The Royal Chemical Society. Figure 4.31 LCST behavior of PNIPAM, tpy‐PNIPAM (32), and [Fe(32)2]X2 with different counterions X (i.e. Cl−, AcO−, and PF6−) in water as monitored by transmittance measurements. Images of the vials below (top) and above the LCST (bottom) are also shown for 32 (left) and [Fe(32)2]2+ (right). Source: Chiper et al. [239]. © 2008 Wiley‐VCH. Figure 4.32 (a) Transmission electron microscopy (TEM) image of PEG–[Ru]–PS micelles in water (without staining). Source: Lohmeijer et al. [216]. Figure reproduced with kind permission. © 2004 The Royal Chemical SocietyFigure 4.33 Representative AFM images of a spin‐coated film (75 nm thickness) of PS375–[Ru]–PEG225 on a Si substrate, before (a) and after (b) the removal of the hydrophilic block. (c) XPS signature (C1s regime) of the film before (solid line) and after treatment with the oxidizing agent. Source: Fustin et al. [220]. Figure reproduced with kind permission. © 2005 Wiley‐VCH.Figure 4.34 Schematic representation of the macroligands33 and 34, which gave an A–[M]–B diblock copolymer in the presence of Zn(II) ions. The diblock copolymer assembled further into spheres and fibers as a function of m/n ratio (m: length of the PEG block, n: length of the P3HT block). Typical TEM images for both cases (i.e. low and high contents of P3HT, respectively) are also shown. Source: He et al. [247]. Figure reproduced