Metallo-Supramolecular Polymerization: A Route to Easy-To-Process Organic/Inorganic Hybrid Materials

Burnworth, Mark; Knapton, Daniel; Rowan, Stuart J.; Weder, Christoph

doi:10.1007/s10904-006-9075-2

Cited by 79 publications

(50 citation statements)

References 108 publications

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“…[100] Although virtually unlimited MCPs can be produced using this technique, the resultant polymers are often poorly soluble and, as such, face difficulties in characterization and further development as functional materials. Such problems arise from the intrinsic skeletal rigidity of coordination units.…”

Section: Coordination and Organometallic Chain Polymersmentioning

confidence: 99%

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Wang¹,

McHale²

2010

Macromol. Rapid Commun.

113

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The incorporation of metallic units into polymer chains has emerged as a promising route towards functional metal-containing (nano)materials. The resulting polymers possess rich functions derived from their metallic elements, such as redox, optical, catalytic and magnetic properties. In addition, the directional and dynamic nature of metal coordination interactions provides further variables for the exploration of novel materials with designed nanostructures. These types of polymers can be synthesized through direct metal-ligand coordination or chain polymerization of metal containing monomers. Depending on the polymerization techniques and starting components, the resulting polymers, akin to their organic counterparts, can be produced in the form of insoluble networks, processible chain structures, gels or colloids. Research into this rising multidisciplinary subject has benefited from recent progress in several related areas such as supramolecular chemistry, colloidal chemistry etc., with the combination of the relative merits of each ensuring further developments in each individual discipline. For example, as a result of studies into organometallic block copolymers self-assembly behavior, living supramolecular polymerization has been unprecedentedly realized for the architectural design of micelles (see image on the right). Nevertheless, the field is still in a developmental stage and offers ample opportunities for fundamental research, as well as material exploration. In this Feature Article, we intend to overview the field with a brief survey of recent literature.

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Section: Coordination and Organometallic Chain Polymersmentioning

confidence: 99%

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Wang¹,

McHale²

2010

Macromol. Rapid Commun.

113

View full text Add to dashboard Cite

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“…For example, Meijer et al employed hydrogen-bonding arrays to form supramolecular polymers of high molecular weight. [17][18][19] Besides hydrogen bonding, metal-ligand interactions [20][21][22] can also drive supramolecular polymerization because of their high binding affinity. On the other hand, concentration is another factor that determines supramolecular polymerization.…”

Section: Introductionmentioning

confidence: 99%

Host‐Enhanced π–π Interaction for Water‐Soluble Supramolecular Polymerization

Liu

Wang

et al. 2011

Chemistry A European J

114

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Host-enhanced π-π interaction based on anthracene derivatives and cucurbit[8]uril can be used as the driving force for constructing water-soluble supramolecular polymers. For this purpose, two anthracene moieties were encapsulated into one cucurbit[8]uril cavity, forming a ternary complex. After encapsulation in the host, the distance between the two anthracene moieties was shortened, and the π-π interaction between them was enhanced significantly. To realize supramolecular polymerization, a bifunctional monomer consisting of two anthracene moieties and a short linker in between was carefully designed. Cyclization was avoided in this way. Thus, host-enhanced π-π interaction can function as a new driving force for supramolecular polymerization.

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“…This design was based on the assumption that the hydrophobic core and the polar metal-ligand motif would phase separate 16 . Metal-Mebip complexes were previously used to self-assemble polymeric materials [17][18][19][20][21] , and their optical properties seemed appropriate for optical healing 22 (see below). To probe how the metal ion affects the materials' properties, 3 was self-assembled with Zn(NTf 2 ) 2 Published in " " which should be cited to refer to this work.…”

mentioning

confidence: 99%

Optically healable supramolecular polymers

Burnworth

Tang

Kumpfer

et al. 2011

Nature

Self Cite

1,633

1,327

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Polymers with the ability to repair themselves after sustaining damage could extend the lifetimes of materials used in many applications 1 . Most approaches to healable materials require heating the damaged area [2][3][4] . Here we present metallosupramolecular polymers that can be mended through exposure to light. They consist of telechelic, rubbery, low-molecular-mass polymers with ligand end groups that are non-covalently linked through metal-ion binding. On exposure to ultraviolet light, the metal-ligand motifs are electronically excited and the absorbed energy is converted into heat. This causes temporary disengagement of the metal-ligand motifs and a concomitant reversible decrease in the polymers' molecular mass and viscosity 5 , thereby allowing quick and efficient defect healing. Light can be applied locally to a damage site, so objects can in principle be healed under load. We anticipate that this approach to healable materials, based on supramolecular polymers and a light-heat conversion step, can be applied to a wide range of supramolecular materials that use different chemistries.The healing of cracks in amorphous polymers by heating above the glass transition temperature (T g ) involves surface rearrangement and approach of polymer chains, followed by wetting, diffusion and reentanglement of the chains 6 . Because the rates of the final two steps are inversely proportional to the molecular mass, healing is generally slow and inefficient. This problem can be overcome by exploiting thermally reversible, covalent bonds 7,8 or non-covalent supramolecular motifs 5,9,10 that allow the reaction equilibrium to be temporarily shifted to lower-molecular-mass species 11 on exposure to heat. This reduces the viscosity of the material, such that defects can be mended, before the equilibrium is shifted back and the polymer is reformed. Supramolecular polymers that phase separate into physically crosslinked networks (Fig. 1a) should be especially well suited for this purpose, because such morphologies generally bestow the material with high toughness. The supramolecular motifs can disengage in the solid state on exposure to heat or a competitive binding agent 12,13 , causing disassembly into small molecules 14 and viscosity reductions. Reporting a series of supramolecular materials formed by metal-ligand interactions, we demonstrate here that this architecture is an excellent basis for elastomeric materials in which defects can be efficiently repaired. We show that the use of light 15 as a stimulus for the dissociation of supramolecular motifs has distinct advantages over thermally healable systems, including the possibility of exclusively exposing and healing the damaged region.The new polymers are based on a macromonomer comprising a rubbery, amorphous poly(ethylene-co-butylene) core with 2,6-bis(19-methylbenzimidazolyl)pyridine (Mebip) ligands at the termini (Fig. 1b, 3). This design was based on the assumption that the hydrophobic core and the polar metal-ligand motif would phase separate 16 . Metal-Mebip com...

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Metallo-Supramolecular Polymerization: A Route to Easy-To-Process Organic/Inorganic Hybrid Materials

Cited by 79 publications

References 108 publications

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Host‐Enhanced π–π Interaction for Water‐Soluble Supramolecular Polymerization

Optically healable supramolecular polymers

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