Fullerene‐Containing Supramolecular Polymers

Haino, Takeharu

doi:10.1002/9783527628742.ch9

Cited by 4 publications

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References 112 publications

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“…Supramolecular polymers with incorporated fullerene have attracted interest in construction of functionalized supramolecular polymers, due to their unique physical and chemical properties . It was found that a π-extended analogue of tetrathiafulvalene (exTTF) could act as a receptor for C 60 .…”

Section: Driving Forces For Supramolecular Polymersmentioning

confidence: 99%

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions

et al. 2015

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Section: Driving Forces For Supramolecular Polymersmentioning

confidence: 99%

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions

et al. 2015

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Supramolecular Cross‐Linking of [60]Fullerene‐Tagged Polyphenylacetylene by the Host–Guest Interaction of Calix[5]arene and [60]Fullerene

et al. 2010

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The cross-linking of polymeric chains is one of the most important topics in polymer science. The cross-linking of linear polymers creates three-dimensional networks and reduces structural flexibility, leading to dramatic changes in macroscopic morphologies and properties. [1] These are irreversible because the three-dimensional networks are constructed with covalent bonds. The introduction of a reversible nature into polymer cross-linkage should generate a new class of intelligent polymer materials; their macroscopic properties might be turned "on" and "off" by external stimuli.The reversible nature of the cross-linkages can be realized by employing noncovalent bonds. Grafting of supramolecular entities onto conventional polymeric scaffolds can produce a cross-linked three-dimensional polymer network with noncovalent bonds. Complementary hydrogen bonding, [2] salt bridges, [3] and metal-ligand interactions [4] produced stably cross-linked polymers, which displayed unusual behaviors and properties. Development of a new supramolecular crosslinkage offers an alternative way to control the three-dimensional structures of cross-linked polymer networks. The crosslinkages driven by host-guest interactions are limited to date. [5] Thus, much work remains to be done to develop a new class of supramolecular cross-linkages with specific hostguest interactions.Fullerene and its analogues are an intriguing class of molecules owing to their unique physical and chemical properties. Fullerene-containing supramolecular polymers that self-assemble through host-guest interactions have been occasionally reported. [6] Our group has been developing fullerene hosts based on a calix[5]arene. During the course of these studies, we found that covalently linked double calix [5]arenes encapsulate fullerenes in their cavities to form 1:1 host-guest complexes. [7] The molecular association between a C 60 molecule and a double-calix[5]arene is strong enough to create a supramolecular polymeric array of [60]fullerenes. [8] We set out to make use of this unique hostguest motif as a new class of supramolecular cross-linkage between polymer chains. Homoditopic host 2 [8a] has two double-calix[5]arene units, each of which can encapsulate a C 60 moiety grafted onto an adjacent polymer chain to create a stable noncovalent cross-linkage. Herein, we present the supramolecular cross-linking of [60]fullerene-tagged polyphenylacetylene poly-1 a, which is established by the hostguest complexation of 2 in an interchain manner ( Figure 1); this process alters the molecular weight and solid-phase morphology of the original polymer.A rhodium catalyst, [{Rh(nbd)Cl} 2 ] (nbd = norbornadiene), is known to effectively polymerize phenylacetylenes to give high-molecular weight, stereoregular polyphenylacetylenes. [9] The copolymerization of phenylacetylenes 3 and 4 at a feed ratio of [3]/([3] + [4]) = 0.9 proceeded smoothly under rhodium catalysis in chlorobenzene to give poly-1 a in 51 % yield. [10] Poly-1 a was composed of 3 and 4 in a ratio of 93:7, as determ...

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Supramolecular Cross‐Linking of [60]Fullerene‐Tagged Polyphenylacetylene by the Host–Guest Interaction of Calix[5]arene and [60]Fullerene

et al. 2010

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The cross-linking of polymeric chains is one of the most important topics in polymer science. The cross-linking of linear polymers creates three-dimensional networks and reduces structural flexibility, leading to dramatic changes in macroscopic morphologies and properties.[1] These are irreversible because the three-dimensional networks are constructed with covalent bonds. The introduction of a reversible nature into polymer cross-linkage should generate a new class of intelligent polymer materials; their macroscopic properties might be turned "on" and "off" by external stimuli.The reversible nature of the cross-linkages can be realized by employing noncovalent bonds. Grafting of supramolecular entities onto conventional polymeric scaffolds can produce a cross-linked three-dimensional polymer network with noncovalent bonds. Complementary hydrogen bonding, [2] salt bridges, [3] and metal-ligand interactions [4] produced stably cross-linked polymers, which displayed unusual behaviors and properties. Development of a new supramolecular crosslinkage offers an alternative way to control the three-dimensional structures of cross-linked polymer networks. The crosslinkages driven by host-guest interactions are limited to date.[5] Thus, much work remains to be done to develop a new class of supramolecular cross-linkages with specific hostguest interactions.Fullerene and its analogues are an intriguing class of molecules owing to their unique physical and chemical properties. Fullerene-containing supramolecular polymers that self-assemble through host-guest interactions have been occasionally reported.[6] Our group has been developing fullerene hosts based on a calix [5]arene. During the course of these studies, we found that covalently linked double calix [5]arenes encapsulate fullerenes in their cavities to form 1:1 host-guest complexes. [7] The molecular association between a C 60 molecule and a double-calix [5]arene is strong enough to create a supramolecular polymeric array of [60]fullerenes. [8] We set out to make use of this unique hostguest motif as a new class of supramolecular cross-linkage between polymer chains. Homoditopic host 2[8a] has two double-calix[5]arene units, each of which can encapsulate a C 60 moiety grafted onto an adjacent polymer chain to create a stable noncovalent cross-linkage. Herein, we present the supramolecular cross-linking of [60]fullerene-tagged polyphenylacetylene poly-1 a, which is established by the hostguest complexation of 2 in an interchain manner ( Figure 1); this process alters the molecular weight and solid-phase morphology of the original polymer.A rhodium catalyst, [{Rh(nbd)Cl} 2 ] (nbd = norbornadiene), is known to effectively polymerize phenylacetylenes to give high-molecular weight, stereoregular polyphenylacetylenes.[9] The copolymerization of phenylacetylenes 3 and 4 at a feed ratio of [3]/([3] + [4]) = 0.9 proceeded smoothly under rhodium catalysis in chlorobenzene to give poly-1 a in 51 % yield.[10] Poly-1 a was composed of 3 and 4 in a ratio of 93:7, as determined ...

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Fullerene‐Containing Supramolecular Polymers

Cited by 4 publications

References 112 publications

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions

Supramolecular Polymers: Historical Development, Preparation, Characterization, and Functions

Supramolecular Cross‐Linking of [60]Fullerene‐Tagged Polyphenylacetylene by the Host–Guest Interaction of Calix[5]arene and [60]Fullerene

Supramolecular Cross‐Linking of [60]Fullerene‐Tagged Polyphenylacetylene by the Host–Guest Interaction of Calix[5]arene and [60]Fullerene

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