Guntram Schwarz

The structure of metallo-supramolecular polyelectrolytes in solution and on surfaces

Metal ion induced self-assembly of the rigid ligand 1,4-bis(2,2′:6′,2″-terpyridine-4′-yl)benzene (1) with Fe(II), Co(II), Ni(II) and Zn(II) acetate in aqueous solution results in extended, rigid-rod like metallosupramolecular coordination polyelectrolytes (MEPE-1). Under the current experimental conditions the molar masses range from 1000 g mol−1 up to 500 000 g mol−1. The molar mass depends on concentration, stoichiometry, metal-ion and time. In addition, we present viscosity measurements, small angle neutron scattering and AFM data. We introduce a protocol to precisely control the stoichiometry during self-assembly using conductometry. The protocol can be used with different terpyridine ligands and the above-mentioned metal ions and is of paramount importance to obtain meaningful and reproducible results. As a control experiment we studied the mononuclear 4′-(phenyl)-2,2′:6′,2″-terpyridine (3) complex with Ni(II) and Zn(II) and the flexible ligand 1,3-bis[4′-oxa(2,2′:6′,2″-terpyridinyl)]propane (2) with Ni(II) acetate (Ni-MEPE-2). This ligand does not form extended macro-assemblies but likely ring-like structures with 3 to 4 repeat units. Through spin-coating of Ni-MEPE-1 on a solid surface we can image the MEPEs in real space by AFM. SANS measurements of Fe-MEPE-1 verify the extended rigid-rod type structure of the MEPEs in aqueous solution.

From terpyridine-based assemblies to metallo-supramolecular polyelectrolytes (MEPEs).

Introducing metal ion coordination as bonding motive into polymer architectures provides new structures and properties for polymeric materials. The metal ions can be part of the backbone or of the side-chains. In the case of linear metallo-polymers the repeat unit bears at least two metal ion receptors in order to facilitate metal-ion induced self-assembly. If the binding constants are sufficiently high, macromolecular assemblies will form in a solution. Likewise, polymeric networks can be formed by metal ion induced crosslinking. The metal ion coordination sites introduce dynamic features, e.g. for self-healing or responsive materials, as well as additional functional properties including spin-crossover, electro-chromism, and reactivity. Terpyridines have attracted attention as receptors in metallo-polymers due to their favorable properties. It is well suited to assemble linear rigid-rod like metallo-polymers in case of rigid ditopic ligands. Terpyridine binds a large number of metal ions and are readily functionalized giving rise to a plethora of available ligands as components in metallo-polymers. By the judicious choice of the metal ions, the design of the ligands, the counter ions and the boundary conditions of self-assembly, the final structure and properties of the resulting metallo-polymers can be tailored at all length scales. Here, we review recent activities in the area of metallo-polymers based on terpyridines as central metal ion receptors.

Electrorheological Fluids Based on Metallo-Supramolecular Polyelectrolyte–Silicate Composites

We present an innovative concept for the design of electrorheological fluids (ERF) based on a dispersed phase of rigid-rod-shaped metallo-supramolecular polyelectrolytes (MEPE) intercalated in mesoporous SBA-15 silica. While applying an electric field to this composite dispersed in silicone oil, rheological measurements reveal a strong increase in the storage modulus, indicating the solidification of the fluid. Besides the strong electrorheological effect and the low current densities, we note that the required amount of MEPE is five times lower than in comparable host-guest ERFs. Composites based on mononuclear complexes do not show a comparable electrorheological effect.

X-ray near-edge absorption study of temperature-induced low-spin-to-high-spin change in metallo-supramolecular assemblies.

X-ray absorption near the iron K edge (XANES) was used to investigate the characteristics of temperature-induced low-spin-to-high-spin change (SC) in metallo-supramolecular polyelectrolyte amphiphile complexes (PAC) containing FeN(6) octahedra attached to two or six amphiphilic molecules. Compared to the typical spin-crossover material Fe(phen)(2) (NCS)(2) XANES spectra of PAC show fingerprint features restricted to the near-edge region which mainly measures multiple scattering (MS) events. The changes of the XANES profiles during SC are thus attributed to the structure changes due to different MS path lengths. Our results can be interpreted by a uniaxial deformation of FeN(6) octahedra in PAC. This is in agreement with the prediction that SC is originated by a structural phase transition in the amphiphilic matrix of PAC, but in contrast to Fe(phen)(2) (NCS)(2), showing the typical spin crossover being associated with shortening of all the metal-ligand distances.