Open AccessThe solid-state architecture of a metallosupramolecular polyelectrolyte
Author(s) -
Ute Kolb,
Karsten Büscher,
Christiane A. Helm,
Anne Lindner,
Andreas F. Thünemann,
M. Menzel,
Masayoshi Higuchi,
Dirk G. Kurth
Publication year - 2006
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.0601092103
Subject(s) - monoclinic crystal system , crystallography , macromolecule , nanoscopic scale , polyelectrolyte , chemistry , helix (gastropod) , materials science , chemical physics , nanotechnology , crystal structure , polymer , biochemistry , organic chemistry , ecology , snail , biology
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 (P 21 /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 , andZ = 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.