Supramolecular Polymers and Assemblies. Andreas Winter

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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 with kind permission. © 2017 American Chemical Society.Figure 4.35 Schematic representation of the synthesis of a metallo‐supramolecular polymer with pending MPEG and poly(2‐diisopropylaminoethyl methacrylate) (PDPA) chains on each repeat unit. This material self‐assembled into striped nanosheets in water. A representative TEM image of such a nanosheet is also depicted. Source: Zhang et al. [250]. Figure reproduced with kind permission. © 2020 The Royal Chemical Society. Figure 4.36 Schematic representation of the metallo‐supramolecular modification of tpy‐functionalized micelles via grafting‐onto and cross‐linking methodologies. Source: Refs. [224,251]. © 2008 and 2009 The Royal Chemical Society. Figure 4.37 Schematic representation of the synthesis of the metallo‐supramolecular ABA‐type triblock copolymers 35.Figure 4.38 Schematic representation of the metallo‐supramolecular polymerization of the ditopic ligand 36 in the presence of transition and rare‐earth metal ions. The pictures illustrate the thermoresponsive (a) and the thixotropic behavior (b) of representative combinations of metal ions. Source: Beck and Rowan [253]. Figure reproduced with kind permission. © 2003 American Chemical Society.Figure 4.39 Schematic representation of the metallo‐supramolecular polymerization of rigid bis‐tridentate ligands with Ru(II) ions.Figure 4.40 Schematic representation of the metallo‐supramolecular polymers reported by the Kurth and Higuchi groups. The colors of the metallopolymers in dilute solution are also shown [a: Fe(II), b: Ru(II), and c: Co(II)]. Source: Han et al. [318]. Figure reproduced with kind permission. © 2004 American Chemical Society.Figure 4.41 Representation of the hierarchical self‐assembly of a metallo‐supramolecular polymer by electrostatic self‐assembly processes. (a) Formation of layer‐by‐layer assemblies, (b) formation of core‐shell or hollow particles and (c) formation of metallopolymer‐amphiphile complexes. PSS: poly(styrene sulfonate); PEI: polyethyleneimine; DHP: dihexadecyl phosphonate [298,299,308]. Source: Wild et al. [67]. © 2011 The Royal Chemical Society.Figure 4.42 Schematic representation of selected metallo‐supramolecular polymers assembled from Zn(II) ions and π‐conjugated bis‐terpyridine ligands.Figure 4.43 (a) Mixing triangle of the metallo‐supramolecular polymers 38b, 38c, and 38d. (b) Picture of the corresponding solutions in a quartz microtiter plate (excitation at λ = 365 nm). (c) Position of the observed emission according to the CIE color scheme. Source: Wild et al. [287]. Figure reproduced with kind permission. © 2013 The Royal Chemical Society.Figure 4.44 Schematic representation of the chiral Ru(II)‐ and Fe(II)‐containing metallopolymers 39–42.Figure 4.45 Schematic representation of the bpp‐, btp‐, and pybox‐type ligands 43–46 used for the self‐assembly with Fe(II), Eu(III), Ru(II), and Zn(II) ions.Figure 4.46 Schematic representation of the “scorpionate”‐type metallopolymer [Fe(47)]_n, the SEC trace (UV detector) of the purified polymer is also shown. Source: Qin et al. [366]. Figure reproduced with kind permission. © 2012 Wiley‐VCH.Figure 4.47 Schematic representation of the general structure of poly(metal acetylide)s and poly(metal arylide)s.Figure 4.48 Schematic representation of the polyplatinyne synthesis, according to Hagihara's original protocol.Figure 4.49 Schematic representation of selected examples of polyplatinynes highlighting the broad structural diversity reported in literature.Figure 4.50 Schematic representation of the poly(metal acetylide)s synthesis via metathesis reactions: (a) classical route and (b) extended one‐pot route.Figure 4.51 Schematic representation of Puddephatt's synthesis of Au(I)‐containing polymers 49 and 50.Figure 4.52 Schematic representation of the Au(I)‐containing monomer 51 which assembled into supramolecular fibers due to aurophilic and H‐bonding interactions. A representative TEM image of the obtained fiber network is also shown. Source: Chen et al. [405]. Figure reproduced with kind permission. © 2017 The Royal Chemical Society.Figure 4.53 Schematic representation of metallo‐supramolecular polymers based on pincer‐type binding motives according to (a) Loeb and Shimidzu [408] was well as (b) van Koten et al. [409].Figure 4.54 Schematic representation of two coordination polymers based on Pd(II)‐pincer complexes according to the Craig (51) and the Weck groups (52), respectively.Figure 4.55 (a) Schematic representation of the proposed synthesis of metallopolymer 56 featuring pincer‐type coordination and carbon‐to‐metal bonds. (b) Schematic representation of the metallopolymer 57 featuring bis(triazol‐4‐yl)pyridine coordination and carbon‐to‐metal bonds; a representation of the 3D SEC analysis is also depicted. Source: Schulze et al. [416]. Figure reproduced with kind permission. © 2017 American Chemical Society.Figure 4.56 (a) Schematic representation of metallo‐supramolecular polymers 58, based on Zn(II)‐dpm bis‐complexes. (b) Scanning electron microscopy (SEM) images of the assembly 58 containing an angular ligand in THF (top, inset: 25 μm × 25 μm fluorescence micrograph) and from a 2 : 1 THF/water mixture (bottom). Source: Maeda et al. [419]. Figure reproduced with kind permission; © 2006 American Chemical Society.Figure 4.57 Schematic representation of the Cu(II)‐containing chain‐extended polymers 59 showing LC behavior.Figure 4.58 Schematic representation of the synthesis of linear and branched coordination polymers, incorporating luminescent Znq₂‐ or Alq₃‐type complexes.Figure 4.59 Schematic representation of metallo‐supramolecular polymers 61 and 62.Figure 4.60 Schematic representation of metallo‐supramolecular polymers, based on salen (63) and catechol bis‐complexes (64).Figure 4.61 Structural characteristics of the coordination assemblies obtained from Ln(III) ions and 65, as a function of the concentration. Source: Vermonden et al. [443]. Figure reproduced with kind permission; © 2004 Wiley‐VCH.Figure 4.62 Schematic representation of the ditopic ligand, which was used for the complexation of Eu(III) ions. Photographs of the free‐standing K_n[Eu(66)]_n polymer film upon excitation with 365‐nm‐light – under NEt₃ vapor and upon exposure to HCl gas – are also shown. The comparison of the photoluminescence intensity reveals the switchability between the “ON” and “OFF” state. Source: Sato and Higuchi [445]. Figure reproduced with kind permission. © 2012 The Royal Chemical Society.Figure 4.63 Schematic representation of the synthesis of a white‐light‐emitting heterobimetallic supramolecular polymer. Source: Sato and Higuchi [448]. Figure reproduced with kind permission. © 2019 Elsevier B.V.Figure 4.64 (a) Schematic representation of the heterobimetallic coordination polymer 68. (b) Schematic representation of the tetrathiolate‐based metallopolymers 69 and their electric conductivities.Figure 4.65 Schematic representation of typical polymetallocene structures.Figure 4.66 Schematic representation of the synthesis of the ferrocene‐containing polymers70 (a) and 71 (b) by a metallo‐supramolecular polymerization. Source: Refs [465,466].Figure 4.67 Schematic representation of the generalized structures of polydecker sandwich complexes (Types A and B) as well as linear polymetallocenes (Types C and D). Source: Redrawn from Manners [41].Figure 4.68 Schematic representation of the synthesis of type‐A polydecker complexes incorporating (a) Ni(II) (72) and (b) Rh(II) centers (73). Figure 4.69 Schematic representation of the oligometallocene 74.Figure 4.70 Schematic representation of the synthesis of the homo‐ and heterometallic polydecker assemblies 75.Figure 4.71 Schematic representation of the type‐C polymetallocene 76.

      5 Chapter 5Figure 5.1 Illustration of the interactions between two idealized p atoms as a function of their orientation – two “attractive” geometries and the “repulsive” face‐to‐face‐type geometry are shown. Source: Hunter and Sanders [4]; © 1990 American Chemical Society.Figure 5.2 Schematic representation of the hexa‐peri‐substituted hexabenzocoronenes1 along with the proposed stacking mode. The polarized optical microscopy (POM) (a) and atomic‐force microscopy (AFM) and (b) images of drop‐casted fibers of 1e are also shown. Source: Kastler et al. [12].

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