Metallosupramolecular approach toward functional coordination polymers

Dobrawa, Rainer; Würthner, Frank

doi:10.1002/pola.20997

Cited by 293 publications

(230 citation statements)

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“…| (6) and n ) 2 -14 a -3 ≈ 6.1 × 10 -5 a -3 ) follow each other closely. We note that with an increase of concentration the probability of finding an acceptor located at a bonding distance and within the binding angle of a donor may change, so that ∆S bend and the equilibrium constant for chain growth, K chain , may vary slightly with concentration.…”

Section: Analytical Modelmentioning

confidence: 53%

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Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation

2007

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Using Monte Carlo simulations we study the association of flexible oligomers terminated by a donor and an acceptor group capable of orientationally specific reversible bonding. On the basis of simulation results, we have obtained equilibrium constants for chain growth and ring closure. These constants were employed in an analytical model, which reproduces the large-scale simulation results very well. We also propose an analytical approach which can be used to analyze experimental data or make predictions of molecular weight, chain/ring distributions, etc., which are hard to obtain experimentally. Our simulation and analytical results show that an increase of orientational specificity of reversible bonding decreases the degree of association and molecular weight and leads to the suppression of small rings. As a result the ring-chain crossover concentration (i.e., the concentration at which the number of reversible bonds in chains and rings coincide) decreases and exhibits a maximum as a function of oligomer length N. With a decrease in the energy of reversible association or increase in temperature the ring-chain crossover shifts to lower concentrations and molecular weight either systematically decreases if the system is in the chain-dominated regime (high concentrations) or increases and exhibit a maximum if the system is in ring-dominated regime (low concentrations). Higher orientational specificity of association in combination with a short spacer length ensures a larger value of the molecular weight at its maximum which is reached at lower temperatures and higher oligomer concentrations. These results are supported by recent experimental observations and can be explained based on the oligomer redistribution between chains and rings near the ring-chain crossover.

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Section: Analytical Modelmentioning

confidence: 53%

“…[1][2][3][4][5][6] The self-healing nature and responsiveness of these polymers to temperature, external fields, etc. implies a large range of potential applications in the general area of "smart materials" or in devices that effect energy, electron or ion exchange.…”

Section: Introductionmentioning

confidence: 99%

Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation

2007

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“…[232][233][234][235][236][237][238][239] A number of excellent reviews in this specific area highlight the influence of the ligand metal interaction, solvent polarity and coordination capability on the degree of polymerization and the dynamic properties. [240][241][242][243][244] It is interesting to point out that in noncoordinating solvents coordination polymers can be kinetically inert and behave like conventional covalent polymers, whereas the presences of traces of coordinating solvent or free ligand increases the exchange rate for the metal coordination bond and impart supramolecular behavior such as stimuli-responsive behavior toward external stimuli. The complexation of bidentate ligands with transition metals behave like a step-growth like polymerization, and the 1:1 stoichiometry is key in obtaining large molecular weight polymers (Fig.…”

Section: Highlightmentioning

confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

128

102

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The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

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“…Although polymers based on kinetically inert transition-metal complexes are readily characterized in solution by standard analytical means, polymeric assemblies formed by kinetically labile transition-metal complexes have successfully evaded characterization in solution (5). The overwhelming majority of metal-organic frameworks are isolated and characterized as crystalline solids (6).…”

mentioning

confidence: 99%

The solid-state architecture of a metallosupramolecular polyelectrolyte

Kolb

Büscher

Helm

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

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Self-assembly of Fe(II) and the ditopic ligand 1,4-bis(2,2:6,2؆-terpyridine-4-yl)benzene results in equilibrium structures in solutions, so-called metallosupramolecular coordination polyelectrolytes (MEPEs). It is exceedingly difficult to characterize such macromolecular assemblies, because of the dynamic nature. Therefore, hardly any structural information is available for this type of material. Here, we show that from dilute solutions, where small aggregates predominate, it is possible to grow nanoscopic crystals at an interface. A near atomic resolution structure of MEPE is obtained by investigating the nanoscopic crystals with electron diffraction in combination with molecular modeling. The analysis reveals a primitive monoclinic unit cell (P2 1͞c space group, a ‫؍‬ 10.4 Å, b ‫؍‬ 10.7 Å, c ‫؍‬ 34.0 Å, ␣ ‫؍‬ ␥ ‫؍‬ 90°, ␤ ‫؍‬ 95°, ‫؍‬ 1.26 g͞cm 3 , and Z ‫؍‬ 4). The MEPE forms linear rods, which are organized into sheets. Four sheets intersect the unit cell, while adjacent sheets are rotated by 90°with respect to each other. The pseudooctahedral coordination geometry of the Fe(II) centers is confirmed by Mö ssbauer spectroscopy. The combination of diffraction and molecular modeling presented here may be of general utility to address problems in structural materials science.electron diffraction ͉ Mö ssbauer spectroscopy ͉ molecular modeling ͉ supramolecular chemistry W eak competing interactions provide an efficient and elegant route to self-assemble supramolecular modules in tailored architectures with a tremendous range of value-adding (1) and dynamic (2) properties. Metal ion-assisted self-assembly is one of the major recognition motives in supramolecular chemistry (3). The resulting metallosupramolecular modules possess structural, kinetic, magnetic, optic, electronic, and reactive properties that are relevant for functional devices and materials of technological interest (4).Although polymers based on kinetically inert transition-metal complexes are readily characterized in solution by standard analytical means, polymeric assemblies formed by kinetically labile transition-metal complexes have successfully evaded characterization in solution (5). The overwhelming majority of metal-organic frameworks are isolated and characterized as crystalline solids (6). The diversity of the resulting framework architectures is remarkable (7). Solids with well defined voids with molecular dimensions give an opportunity to manipulate, separate, arrange, and react molecules. Now, there are a large number of porous solids available that exhibit permanent porosity suitable for technological applications (8-10).In 1992, Constable et al. (11) published the synthesis and characterization of various multinucleating terpyridines (tpy), including 1,4-bis(2,2Ј:6Ј,2Љ-terpyridine-4Ј-yl)benzene (11). A high binding affinity to many transition metal ions and a well defined stereochemistry make this building block an attractive component for the assembly of dynamic and functional metallosupramolecular polyelectrolytes (MEPEs) (Scheme 1)...

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Metallosupramolecular approach toward functional coordination polymers

Cited by 293 publications

References 70 publications

Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation

Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation

Controlling supramolecular polymerization through multicomponent self‐assembly

The solid-state architecture of a metallosupramolecular polyelectrolyte

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