Water-Soluble Reversible Coordination Polymers:  Chains and Rings

Vermonden, Tina; Gucht, Jasper van der; Waard, Pieter de; Marcelis, Antonius T. M.; Besseling, N.A.M.; Sudhölter, Ernst J. R.; Fleer, G.J.; Stuart, Martien A. Cohen

doi:10.1021/ma030353t

Cited by 146 publications

(223 citation statements)

References 29 publications

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“…5,24 We note that observed increase in viscosity can also be attributed to the change in the chain architecture from rings to chains. On the basis of 1 H NMR data, the increase in viscosity is accompanied by a 4-5 times increase in chain population 20,24 which agrees with our results (for B ) 5) of about a 5 times increase in chain fraction upon temperature increase (Figure 10, inset). This confirms that an increase in M w is due to shift of the equilibrium from rings to chains.…”

Section: Resultssupporting

confidence: 91%

“…While solution of the proposed equations is rather straightforward, to obtain so many equilibrium constants from experimental measurements is rather cumbersome, taking into account that even the determination of the molecular weight represents a challenge for such "living" polymers. 5,19 Another technical problem is that the ring-chain equilibrium constant for larger rings is often theoretically estimated based on Gaussian statistics, 7,11,16,17,20,21 although supramolecular polymers formed by self-assembly of a flexible spacers in a good solvent often behave more like chains with excluded volume than Gaussian chains. Associating monomers with excluded volume have been studied in considerable detail in computer simulations, 12,13,15,22,23 although in these cases orientational specificity either was not considered 22,23 or it was applied to all monomers (oligomer size one).…”

Section: Introductionmentioning

confidence: 99%

“…For instance, the experimentally observed increase in viscosity with temperature 5,24 was either explained based on analogy with ringopening polymerization or using a combination of equilibrium constants as fitting parameters for an analytical model employing Gaussian statistics for rings, which would qualitatively agree with experimental results. 20 Still a detailed theoretical consideration of this effect for supramolecular polymers, exhibiting some excluded volume effects and more importantly having different rigidity of spacers compared to associating groups, is lacking.…”

Section: Introductionmentioning

confidence: 99%

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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: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

2007

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“…A pyridine ring carrying two carboxylic acid groups turned out to be a good ligand; a wide range of metal ions could form a bidentate complex with two such ligands, so that two such ligands connected back-to-back by a suitable spacer (denoted as 'L 2 EO n ') should be able to form water-soluble coordination polymers (Fig. 2) [9]. This turned out to be the case: at the proper (1:2) metal/ ligand ratio (e.g., with Zn as the coordinated metal), chains were found in the solution.…”

Section: Reversible Supramolecular Polymersmentioning

confidence: 99%

Supramolecular perspectives in colloid science

Stuart

2008

Colloid Polym Sci

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Supramolecular chemistry puts emphasis on molecular assemblies held together by non-covalent bonds. As such, it is very close in spirit to colloid science which also focuses on objects which are small, but beyond the molecular scale, and for which other forces than covalent bonds are crucial. We discuss in this review the preparation and properties of new colloidal systems which borrow on the one hand from classical topics in colloid science, such as micellization, and on the other hand from concepts in supramolecular chemistry, such as reversible supramolecular polymers.

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“…The mean molar mass of the assemblies depends on the concentrations of the constituents and is determined by the dynamic equilibrium of association and dissociation. On increasing the concentration, the mean length is shifted to larger assemblies (23). The theory of self-assembly of two components predicts an exponential growth as a function of concentration.…”

mentioning

confidence: 98%

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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Water-Soluble Reversible Coordination Polymers: Chains and Rings

Cited by 146 publications

References 29 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

Supramolecular perspectives in colloid science

The solid-state architecture of a metallosupramolecular polyelectrolyte

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