title: The solid-state architecture of a metallosupramolecular polyelectrolyte.
abstract: 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(1)/c space group, a = 10.4 A, b = 10.7 A, c = 34.0 A, alpha = gamma = 90 degrees , beta = 95 degrees , rho = 1.26 g/cm(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 degrees with respect to each other. The pseudooctahedral coordination geometry of the Fe(II) centers is confirmed by Mössbauer spectroscopy. The combination of diffraction and molecular modeling presented here may be of general utility to address problems in structural materials science.
authors.affiliation: Institut für Physikalische Chemie, Johannes Gutenberg-Universität, Welderweg 11, D-55099 Mainz, Germany.
authors.forename: Ute
authors.initials: U
authors.lastname: Kolb
authors.affiliation: Institut für Physik, Ernst-Moritz-Arndt Universität, Friedrich-Ludwig-Jahn-Strasse 16, D-17489 Greifswald, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Büscher
authors.affiliation: Institut für Physik, Ernst-Moritz-Arndt Universität, Friedrich-Ludwig-Jahn-Strasse 16, D-17489 Greifswald, Germany.
authors.forename: Christiane A
authors.initials: CA
authors.lastname: Helm
authors.affiliation: Max Planck Institute of Colloids and Interfaces, D-14424 Potsdam, Germany; and.
authors.forename: Anne
authors.initials: A
authors.lastname: Lindner
authors.affiliation: Bundesanstalt für Materialforschung and -prüfung, Richard-Willstaeter Strasse11, D-12489 Berlin, Germany.
authors.forename: Andreas F
authors.initials: AF
authors.lastname: Thünemann
authors.affiliation: Bundesanstalt für Materialforschung and -prüfung, Richard-Willstaeter Strasse11, D-12489 Berlin, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Menzel
authors.affiliation: National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
authors.forename: Masayoshi
authors.initials: M
authors.lastname: Higuchi
authors.affiliation: Max Planck Institute of Colloids and Interfaces, D-14424 Potsdam, Germany; and kurth@mpikg.mpg.de.|National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
authors.forename: Dirk G
authors.initials: DG
authors.lastname: Kurth