0000000000459335
AUTHOR
Ulrich Ziener
Two-Level Self-Organisation of Arrays of [2×2] Grid-Type Tetranuclear Metal Complexes by Hydrogen Bonding
Here we report on the synthesis and characterisation of four new complexes of the [2×2] M4II grid-type (M = Co, Fe, Zn) with oligopyridine-derived ligands. The presence of aminopyrazine and aminopyrimidine moieties at the edge of the ligands potentially enables the formation of infinite hydrogen-bonded multi-grid networks. The ligands were synthesised by subsequent stannylations and Stille-type coupling reactions. The complexes were obtained by self-assembly of the ligand with the metal salt. The single-crystal X-ray structure was determined for the Co complex 7 containing aminopyrimidine as the hydrogen-bonding moiety [P1¯; a = 15.4976(4), b = 18.2114(6), c = 31.9538(10) A, α = 86.9809(13)…
Hierarchical Self-Assembly of Supramolecular Spintronic Modules into 1D- and 2D-Architectures with Emergence of Magnetic Properties
Hierarchical self-assembly of complex supramolecular architectures allows for the emergence of novel properties at each level of complexity. The reaction of the ligand components A and B with Fe II cations generates the (2 K 2) grid-type functional building modules 1 and 2, presenting spin-tran- sition properties and preorganizing an array of coordination sites that sets the stage for a second assembly step. Indeed, binding of La III ions to 1 and of Ag I ions to 2 leads to a 1D columnar superstructure 3 and to a wall-like 2D layer 4, respectively, with concomitant modulation of the magnetic properties of 1 and 2. Thus, to each of the two levels of structural complexity generat- ed by the t…
Recognition-Directed Supramolecular Assemblies of Metal Complexes of Terpyridine Derived Ligands with Self-Complementary Hydrogen Bonding Sites
The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but p…