Generation of metallosupramolecular polymer gels from multiply functionalized grid-type complexes

Hardy, John G.; Cao, Xiaoyu; Harrowfield, Jack; Lehn, Jean‐Maríe

doi:10.1039/c2nj20898a

Cited by 16 publications

(18 citation statements)

References 53 publications

(32 reference statements)

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“…An important factor limiting the use of these self‐assembled structures so far is the lack of functionalization of the BTP scaffold, reducing opportunities for targeted interaction and further reactions. For the related bishydrazone ligands, a few examples of functionalized ligands and resulting functionalized grid complexes were published by Chmielewski et al, Drożdż et al and Hardy et al demonstrating the potential of multivalent grid complexes for biomedical and material applications . While the introduction of new functionalities to the ligand is obviously of great interest, this can interfere with grid formation as some authors have reported .…”

Section: Introductionmentioning

confidence: 99%

Optically Functionalized Grid‐Type Complexes by a Post‐Assembly Strategy

Eggers

Ziener

2018

Chemistry A European J

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Bisterpyridine-based grid complexes can serve as supramolecular three-dimensional scaffolds for the construction of larger molecular assemblies. Through functionalization of the ligand with azide groups, followed by self-assembly and metal-free Huisgen reactions, eight pyrene molecules can be attached to the grid structure in a single reaction step. The orientation and proximity provided by the scaffold allows for tuning the fluorescence properties of the dye molecules.

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Section: Introductionmentioning

confidence: 99%

Optically Functionalized Grid‐Type Complexes by a Post‐Assembly Strategy

Eggers

Ziener

2018

Chemistry A European J

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“…[23][24][25][26][27][28][29] Inspired by this structural versatility and potential applications such as mechanical enhancement, catalysis, encapsulation, sensing, etc., much effort has been recently devoted to installing MOCs into polymer networks to provide 'polyMOC' hybrid materials with tunable viscoelasticity and functionality. [30][31][32][33][34][35][36][37] One [30,[38][39][40][41][42] ; however, there is still a great need to understand how polyMOC microstructure translates to bulk material properties such as modulus and relaxation dynamics. To accomplish this goal, robust, modular polyMOC synthesis strategies that enable access to a wide range of structures and properties are needed.…”

Section: Introductionmentioning

confidence: 99%

Star PolyMOCs with Diverse Structures, Dynamics, and Functions by Three‐Component Assembly

Wang

Keeler

et al. 2016

Angewandte Chemie

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We report star polymer metal-organic cage (polyMOC) materials whose structures, mechanical properties, functionalities, and dynamics can all be precisely tailored through a simple threecomponent assembly strategy. The star polyMOC network is composed of tetra-arm star polymers functionalized with ligands on the chain ends, small molecule ligands, and palladium ions; polyMOCs are formed via metal-ligand coordination and thermal annealing. The ratio of small molecule ligands to polymer-bound ligands determines the connectivity of the MOC junctions and the network structure. The use of large M 12 L 24 MOCs enables great flexibility in tuning this ratio, which provides access to a rich spectrum of material properties including tunable moduli and relaxation dynamics. HHS Public Access Author Manuscript Author ManuscriptAuthor Manuscript Author ManuscriptA three-component assembly strategy is reported that enables the creation of a versatile class of polymer metal-organic cage (polyMOC) networks with tailored microstructures, mechanical properties, functionalities, and network dynamics. KeywordsMetal-organic cage; Metal-organic polyhedra; Polymer network; Metallosupramolecular assembly; Gel; PolyMOC Polymer networks are versatile materials with a wide range of structures and properties suitable for industrial and academic applications. [1][2][3] In a typical network, macromolecules of choice are connected to branched junctions of a particular type; the nature of these components determines the material's properties such as stiffness, toughness, responsiveness, etc. [2] Several strategies have been developed to tune polymer network structure in order to realize desirable properties. For example, interpenetrating networks, [4][5] nanocomposites, [6] and reversible and/or dynamic covalent bonds [7] are employed to yield materials with self-healing, stimuli-responsive, and other valuable behaviors. [7][8] In all of these cases, control over network structure and dynamics is critical. In this communication, we describe a versatile and simple strategy for controlling structure, function, and dynamics in a relatively new class of polymer networks that is based on the use of large metal-organic cages/polyhedra (MOCs).MOCs are discrete 3D structures assembled from x metal ions and y organic ligands via coordination bonds. [9][10][11][12][13][14][15][16][17][18][19][20][21][22] By rational design of the ligands and proper choice of the metal ions, MOCs of different M x L y stoichiometries, sizes, and geometries can be synthesized. [23][24][25][26][27][28][29] Inspired by this structural versatility and potential applications such as mechanical enhancement, catalysis, encapsulation, sensing, etc., much effort has been recently devoted to installing MOCs into polymer networks to provide 'polyMOC' hybrid materials with tunable viscoelasticity and functionality. [30][31][32][33][34][35][36][37] One [30,[38][39][40][41][42] ; however, there is still a great need to understand how polyMOC microstructure translates to bulk ...

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“…1 This interest has grown from the founding work developing organic gelators 2 to include metallogelators, inorganic species capable of sustaining hydro-and organogels. 7 Examples utilising non-covalent interactions encompass Au···Au or Pt···Pt interactions, 8 and typically such complexes tether several long alkyl chains to aid facilitation of the gelation process. Typically two strategies are employed to generate metallogels; these target either coordination polymeric gelators, or discrete metal complexes able to adopt fibrillar constructs with the aid of metallophilic, van der Waals, and other non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%

A new small molecule gelator and 3D framework ligator of lead(ii)

et al. 2015

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Reacting equimolar quantities of 5-allenyl-1,3-benzenedicarboxylic acid (H2abd) with lead(II) acetate trihydrate in N,N-dimethylformamide (DMF) under solvothermal conditions results in formation of a metallogel with a critical gelation percentage of 1% w/v. Elemental analysis performed on the gel provided a molecular composition ratio of [Pb(abd)(H2O)]n (1). Viewing the gel by scanning electron microscopy (SEM) identified an entangled network of cross-linked nano-fibres. 1 H-NMR aliquots of hydrated lead(II) acetate added to a solution of H2abd in deuterated DMF allow inferences to be made about solution-state behaviour that occurs during the initial gel aggregation stage. Under nonsolvothermal conditions, combining H2abd and hydrated lead(II) acetate resulted in formation of single crystals suitable for X-ray diffraction, which were identified as a 3D coordination polymer with composition [Pb(abd)(DMF)] (2). Structural features observed within this 3D coordination polymer provide the basis for assigning the molecular structure to the fibrils present within gel 1. This assertion is supported by comparable vibrational profiles taken from a sample of dried gel 1 to that of crystalline 2, and the matching of early solution-state 1 H-NMR spectroscopic trends to later solid-state observations.A new allene dicarboxylate ligand reacts with hydrated lead(II) acetate in DMF to yield either a crystalline 3D framework or a metallogel dependent on the reaction temperature.

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Generation of metallosupramolecular polymer gels from multiply functionalized grid-type complexes

Abstract: Hardy, J. G., Cao, X., Harrowfield, J., & Lehn, J-M. (2012). Generation of metallosupramolecular polymer gels from multiply functionalized grid-type complexes.

Cited by 16 publications

References 53 publications

Optically Functionalized Grid‐Type Complexes by a Post‐Assembly Strategy

Optically Functionalized Grid‐Type Complexes by a Post‐Assembly Strategy

Star PolyMOCs with Diverse Structures, Dynamics, and Functions by Three‐Component Assembly

A new small molecule gelator and 3D framework ligator of lead(ii)

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