Synthesis and characterisation of dense ferroic frameworks Thomas Hitchings 1 and Paul Saines 1, Helen Wickins, 2 George Peat 2 , Paul Hodgkinson 2 , Anant Kumar Srivastava 2 , Ross Piltz 1 , Franz Demmel 3 , Richard J. Dixey 4 , Anthony Phillips 5 1 University of Kent, UK, Durham University, UK, 3 Australian Nuclear Science and Technology Organisation, Australia, 4 ISIS Facility, Rutherford Appleton Laboratory, UK 5 Queen Mary University of London, UK Metal-organic frameworks have been studied extensively for their material properties rooted in the intrinsic porosity achieved by coordinating a diverse range of organic linkers to metal cations. Using short organic linkers minimises this porosity and can give material properties closer to that of well-studied inorganic systems, like metal oxides. The design flexibility of the frameworks, coupled with the material properties of inorganic systems, allows design and synthesis of new dense frameworks based on existing inorganic archetypes. The density of these frameworks is a key design parameter when looking for ferroic properties, such as ferromagnetism and ferroelectricity, as the separation of the magnetic centres directly impacts magnetic coupling. 1,2 Any porosity generated by short linkers can be occupied by a guest cation, analogous to the A-site cation of a perovskite- like system. The geometry of the framework structures also dictates material properties, with formate-based frameworks commonly crystalising in non-centrosymmetric polar point groups, which is essential for ferroelectric properties. 3 By utilising these design rules, a range of dense ferroic framework materials have been synthesised and investigated for their magnetic and ferroelectric properties through a broad range of characterisation techniques including crystallography, NMR and neutron scattering. By intricately adjusting design parameters of these systems, the structure-property relationships that dictate the ferroic behaviour of these dense frameworks have been studied and understood.
Figure 1 . Dense frameworks sitting at the interface between conventional inorganic systems and metal-organic frameworks. References 1. R. J. C. Dixey and P. J. Saines, Inorg. Chem. , 2018, 57 , 12543–12551. 2. R. J. C. Dixey, G. B. G. Stenning, P. Manuel, F. Orlandi and P. J. Saines, J. Mater. Chem. C , 2019, 7 , 13111–13119. 3. P. S. Halasyamani and K. R. Poeppelmeier, Chem. Mater. , 1998, 10 , 2753–2769.
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