Metallosupramolecular Thin Polyelectrolyte Films

Schütte, Markus; Kurth, Dirk G.; Linford, Matthew R.; Cölfen, Helmut; Möhwald, H.

doi:10.1002/(sici)1521-3773(19981102)37:20<2891::aid-anie2891>3.0.co;2-7

Cited by 180 publications

(113 citation statements)

References 2 publications

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“…13). With oppositely charged macromolecules, MEPEs form films on various substrates, including nanoparticles, held together primarily by electrostatic interactions (14).…”

mentioning

confidence: 99%

A route to hierarchical materials based on complexes of metallosupramolecular polyelectrolytes and amphiphiles

Kurth

Lehmann

Schütte

2000

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

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112

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Anisotropic thin film materials of metallosupramolecular polyelectrolyte-amphiphile complexes (denoted PACs) with structures at several length scales were fabricated through a multistep self-assembly process. Metal ion-mediated self-assembly of the ditopic ligand 1,4-bis(2,2:6,2-terpyridine-4-yl)benzene and electrostatic binding with the amphiphile dihexadecyl phosphate result in a PAC with tailored surface chemical properties, including solubility and surface activity. The PAC forms a stable monolayer at the air-water interface that is readily transferred and oriented on solid supports with the Langmuir-Blodgett technique. The presented strategy unifies colloid and metallosupramolecular chemistry and opens a versatile route to hierarchical materials with tailored structures and functions.T he design and construction of supramolecular architectures of nanoscopic dimensions give access to entities of increasing complexity with distinct structural and functional properties (1). The use of intermolecular forces provides a rational and efficient method to position molecular components precisely in a well defined supramolecular architecture (2). Self-assembly relies on a sequence of spontaneous recognition, growth, and termination steps to form the final equilibrium supramolecular entity (or a collection of such) through metal ion coordination, hydrogen bonds, or hydrophobic or electrostatic interactions. Applications of such systems in materials science, medicine, and chemical technology are diverse, including recognition (sensing), transformation (catalysis), and translocation (signal transduction) devices.Although the principles that govern self-assembly of discrete supramolecular assemblies are well understood, the fabrication of (extended) structures with more than one length scale is the next challenge in the implementation of supramolecular devices in functional materials (3). Correlation of positions and orientations of the constituents in a material, preferentially over a long range, is of paramount importance to exploit the properties of supramolecular devices fully, for example in vectorial transport processes, such as light-to-energy conversion, or to establish an electronic band structure as in semiconductors (4 -6). To achieve this goal, it will be necessary to improve existing and to innovate new methods to fabricate hierarchical materials. The Langmuir-Blodgett (LB) technique was one of the first methods to fabricate films with a well defined architecture and played a key role in the development of molecular electronics (7). Other approaches include the engineering of crystals (8), liquid crystalline materials, and lyotropic mesophases (9). However, the implementation of metallosupramolecular devices in ordered hierarchical architectures has not been realized to date.Metal-ion-directed self-assembly is of particular interest for the construction of functional devices (10). Metal ions possess a range of well defined coordination geometries and diverse properties that are relevant in electronic and phot...

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“…13). With oppositely charged macromolecules, MEPEs form films on various substrates, including nanoparticles, held together primarily by electrostatic interactions (14).…”

mentioning

confidence: 99%

A route to hierarchical materials based on complexes of metallosupramolecular polyelectrolytes and amphiphiles

Kurth

Lehmann

Schütte

2000

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

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112

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“…The ligand (11) and MEPE (12) were prepared according to literature procedures. Solid MEPE was prepared by precipitation from aqueous solution.…”

Section: Methodsmentioning

confidence: 99%

“…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) (12). The ditopic tpy-ligand used here forms stable macromolecular assemblies in solution, so the availability of processable MEPEs stimulated research concerning nanostructures (13), Langmuir (14) and Langmuir-Blodgett (15) layers, thin films (16), capsules (17) and liquid crystals (18), electrochromic windows (19), rheological fluids (20,21), and magnetic materials (22).…”

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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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“…The first water-soluble MEPEs based on 1,4-bis(2,2 :6 ,2 -terpyridin-4-yl)benzene and Fe(OAc) 2 were reported more than five years after Constable's work and finally opened an avenue to study and employ these systems in many ways (figure 6) [49]. Although the solution structure and the solution properties such as the rheological and polyelectrolyte properties require further studies, the solid-state structure of the MEPE based on FeOAc 2 and 1,4-bis(2,2 :6 ,2 -terpyridin-4-yl)benzene was recently determined by electron diffraction (figure 6).…”

Section: Metallo-supramolecular Polymersmentioning

confidence: 99%

Metallo-supramolecular modules as a paradigm for materials science

Kurth

2008

Science and Technology of Advanced Materials

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Metal ion coordination in discrete or extended metallo-supramolecular assemblies offers ample opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. A key challenge is to improve and develop methodologies for placing these active modules in suitable device architectures, such as thin films or mesophases. This review highlights recent developments in extended, polymeric metallo-supramolecular systems and discrete polyoxometalates with an emphasis on materials science.

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Metallosupramolecular Thin Polyelectrolyte Films

Cited by 180 publications

References 2 publications

A route to hierarchical materials based on complexes of metallosupramolecular polyelectrolytes and amphiphiles

A route to hierarchical materials based on complexes of metallosupramolecular polyelectrolytes and amphiphiles

The solid-state architecture of a metallosupramolecular polyelectrolyte

Metallo-supramolecular modules as a paradigm for materials science

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