3 research outputs found
Dicyanometallates as Model Extended Frameworks
We report the structures
of eight new dicyanometallate frameworks containing molecular extra-framework
cations. These systems include a number of hybrid inorganic–organic
analogues of conventional ceramics, such as Ruddlesden–Popper
phases and perovskites. The structure types adopted are rationalized
in the broader context of all known dicyanometallate framework structures.
We show that the structural diversity of this family can be understood
in terms of (i) the charge and coordination preferences of the particular
metal cation acting as framework node, and (ii) the size, shape, and
extent of incorporation of extra-framework cations. In this way, we
suggest that dicyanometallates form a particularly attractive model
family of extended frameworks in which to explore the interplay between
molecular degrees of freedom, framework topology, and supramolecular
interactions
Dicyanometallates as Model Extended Frameworks
We report the structures
of eight new dicyanometallate frameworks containing molecular extra-framework
cations. These systems include a number of hybrid inorganic–organic
analogues of conventional ceramics, such as Ruddlesden–Popper
phases and perovskites. The structure types adopted are rationalized
in the broader context of all known dicyanometallate framework structures.
We show that the structural diversity of this family can be understood
in terms of (i) the charge and coordination preferences of the particular
metal cation acting as framework node, and (ii) the size, shape, and
extent of incorporation of extra-framework cations. In this way, we
suggest that dicyanometallates form a particularly attractive model
family of extended frameworks in which to explore the interplay between
molecular degrees of freedom, framework topology, and supramolecular
interactions
Guest-Activated Forbidden Tilts in a Molecular Perovskite Analogue
The manipulation of distortions in
perovskite structures is critical
to tailoring the properties of these materials for a variety of applications.
Here we demonstrate a violation of established octahedral tilt rules
in the double perovskite analogue (NH<sub>4</sub>)<sub>2</sub>SrFeÂ(CN)<sub>6</sub>·2H<sub>2</sub>O. The forbidden tilt pattern we observe
arises through coupling to hydration-driven Jahn–Teller-like
distortions of the Sr coordination environment. Access to novel distortion
mechanisms and the ability to switch these distortions on and off
through chemical modification fundamentally expands the toolbox of
techniques available for engineering symmetry-breaking processes in
solid materials