ABSTRACT
We report an extensive study on the coordination behavior of chiral ditopic bridging ligands, which lead to metallosupramolecular polymers in the presence of Zn(II) and Cu(II) in solution. With the help of UV-vis and circular dichroism spectroscopies, we show that the metallopolymer sequence can be controlled by chirality and by the choice of the metal ion. Although the formation of a block metallopolymer proceeds through the assembly of homoleptic complexes, an alternate metallopolymer may be obtained only when heteroleptic complexes are formed. This demonstrates how the prevalent coordination geometries at metal centers may be used to control the sequences of the metallopolymers.
ABSTRACT
The properties of ferroelectric domain walls can significantly differ from those of their parent material. Elucidating their internal structure is essential for the design of advanced devices exploiting nanoscale ferroicity and such localized functional properties. Here, we probe the internal structure of 180° ferroelectric domain walls in lead zirconate titanate (PZT) thin films and lithium tantalate bulk crystals by means of second-harmonic generation microscopy. In both systems, we detect a pronounced second-harmonic signal at the walls. Local polarimetry analysis of this signal combined with numerical modelling reveals the existence of a planar polarization within the walls, with Néel and Bloch-like configurations in PZT and lithium tantalate, respectively. Moreover, we find domain wall chirality reversal at line defects crossing lithium tantalate crystals. Our results demonstrate a clear deviation from the ideal Ising configuration that is traditionally expected in uniaxial ferroelectrics, corroborating recent theoretical predictions of a more complex, often chiral structure.
