TY - JOUR A1 - Kolb, U. A1 - Büscher, K. A1 - Helm, C.A. A1 - Lindner, A. A1 - Thünemann, Andreas A1 - Menzel, Michael A1 - Higuchi, M. A1 - Kurth, D.G. T1 - The solid-state architecture of a metallosupramolecular polyelectrolyte JF - Proceedings of the national academy of sciences of the United States of America N2 - 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 (P21/c space group, a = 10.4 Å, b = 10.7 Å, c = 34.0 Å, α = γ = 90°, β = 95°, ρ = 1.26 g/cm³, 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 Mössbauer spectroscopy. The combination of diffraction and molecular modeling presented here may be of general utility to address problems in structural materials science. KW - Polymer KW - Polyelectrolyte KW - Electron diffraction KW - Mössbauer spectroscopy KW - Molecular modeling KW - Supramolecular chemistry PY - 2006 SN - 0027-8424 SN - 1091-6490 VL - 103 IS - 27 SP - 10202 EP - 10206 PB - National Academy of Sciences CY - Washington, DC AN - OPUS4-12495 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -