TY - JOUR A1 - Bodenthin, Yves A1 - Grenzer, Jörg A1 - Lauter, Robert A1 - Pietsch, Ullrich A1 - Lehmann, Pit A1 - Kurth, Dirk G. A1 - Möhwald, Helmuth T1 - Temperature and time resolved x-ray scattering at thin organic films Y1 - 2002 ER - TY - JOUR A1 - Pietsch, Ullrich A1 - Bodenthin, Yves A1 - Grenzer, Jörg A1 - Geue, Thomas A1 - Möhwald, Helmuth A1 - Kurth, Dirk G. T1 - Structure and temperature behavior of metallo-supramolecular assemblies N2 - A detailed structural analysis of a Langmuir-Blodgett (LB) multilayer composed of a polyelectrolyte-amphiphile complex (PAC) is presented. The PAC is self-assembled from metal ions, ditopic bis-terpyridines, and amphiphiles. The vertical structure of the LB multilayer is investigated by X-ray reflectometry. The multilayer has a periodicity of 57 A, which corresponds to an architecture of flat lying metallo-supramolecular coordination polyelectrolyte (MEPE) rods and upright-standing amphiphiles (dihexadecyl phosphate, DHP). In-plane diffraction reveals hexagonal packing of the DHP molecules. Using extended X-ray absorption fine structure (EXAFS) experiments, we prove that the central metal ion is coordinated to the terpyridine moieties in a pseudo-octahedral coordination environment. The Fe-N bond distances are 1.82 and 2.0 angstrom, respectively. Temperature resolved measurements indicate a reversible phase transition in a temperature range up to 55 degrees C. EXAFS measurements indicate a lengthening of the average Fe-N bond distance from 1.91 to 1.95 angstrom. The widening of the coordination cage upon heating is expected to lower the ligand field stabilization, thus giving rise to spin transitions in these composite materials Y1 - 2005 ER - TY - JOUR A1 - Pietsch, Ullrich A1 - Bodenthin, Yves A1 - Möhwald, Helmuth A1 - Kurth, Dirk G. T1 - Inducing spin crossover in metallo-supramolecular polyelectrolytes through an amphiphilic phase transition N2 - A phase transition in an amphiphilic mesophase is explored to deliberately induce mechanical strain in an assembly of tightly coupled metal ion coordination centers. Melting of the alkyl chains in the amphiphilic mesophase causes distortion of the coordination geometry around the central transition metal ion. As a result, the crystal field splitting of the d-orbital subsets decreases resulting in a spin transition from a low-spin to a high-spin state. The diamagnetic-paramagnetic transition is reversible. This concept is demonstrated in a metallo-supramolecular coordination polyelectrolyte-amphiphile complex self-assembled from ditopic bis-terpyridines, Fe(II) as central transition metal, and dialkyl phosphates as amphiphiles. The magnetic properties are studied in a Langmuir-Blodgett multilayer. The modularity of this concept provides extensive control of structure and function from molecular to macroscopic length scales and gives access to a wide range of new molecular magnetic architectures such as nanostructures, thin films, and liquid crystals Y1 - 2005 ER - TY - JOUR A1 - Schwarz, Guntram A1 - Sievers, Torsten K. A1 - Bodenthin, Yves A1 - Hasslauer, Ires A1 - Geue, Thomas A1 - Koetz, Joachim A1 - Kurth, Dirk G. T1 - The structure of metallo-supramolecular polyelectrolytes in solution and on surfaces N2 - 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 macroassemblies 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. Y1 - 2010 UR - http://pubs.rsc.org/en/content/articlehtml/2010/jm/b926783b U6 - https://doi.org/10.1039/B926783b SN - 0959-9428 ER - TY - JOUR A1 - Schwarz, Guntram A1 - Bodenthin, Yves A1 - Geue, Thomas A1 - Koetz, Joachim A1 - Kurth, Dirk G. T1 - Structure and properties of dynamic rigid rod-like metallo-supramolecular polyelectrolytes in solution N2 - Metal-ion-induced self-assembly in aqueous solution of the rigid ligand 1,4-bis(2,2':6',2 ''-terpyridine-4'-yl)benzene (1) with Fe(OAc)(2) and Ni(OAc)(2) is investigated with viscosimetry, SANS, and AFM. Ligand 1 forms extended, rigid-rod like metallo-supramolecular coordination polyeectrolytes (MEPEs) with a molar mass of up to 200 000 g mol(-1) under the Current experimental conditions. The molar mass depends oil concentration, stoichiometry, and time. By spin-coating MEPEs oil a solid surface, we call image the MEPEs in real space by AFM. Both AFM and SANS confirm the extended rigid-rod-type structure of the MEPEs. As a control experiment, we also studied the flexible ligand 1,3-bis[4'-oxa(2,2':6',2 ''-terpyridinyl)]propane (2). Ligand 2 does not form extended macro-assemblies but likely ringlike structures with three 10 four repeat units. Finally, we present it protocol to control the stoichiometry during self-assembly using conductometry, which is of paramount importance to obtain meaningful and reproducible results. Y1 - 2010 UR - http://pubs.acs.org/doi/full/10.1021/ma902057f U6 - https://doi.org/10.1021/Ma902057f SN - 0024-9297 ER -