magnetic and ferroelectric properties, magnetoelectric coupling effect, metal–organic frameworks, multiferroicity, structural phase transition, Physics, QC1-999, Technology

Abstract Multiferroics have been investigated extensively in the last decades due to their wide range of applications in high‐density multistate storage, spintronics, and novel multifunctional magnetic–electric devices. One peculiar subgroup of multiferroic materials comprises 3D perovskite metal–organic frameworks (MOFs) with the general formula ABX3 (A = monovalent organic cation (such as an alkali metal or protonated amine), B = divalent metal cation, X = organic anion), for their coexistence of multiple orders (electric, magnetic, and elastic, et al.). The purpose of this review is to give a representative overview of the recent progress in the field of ABX3‐type multiferroic MOFs, containing 3d magnetic metal ions at B‐site. First, the perovskite multiferroic MOFs in which X‐site is occupied by formate, is examined and summarized. In particular, magnetoelectric coupling effects, such as electric‐field tuning of magnetic properties and magnetic field control of electric polarization, and pressure control of structural/magnetic/electric properties, are described and discussed. Then, it is focused on the structural phase transitions and ferroic orders by analyzing several representative multiferroic MOFs compounds with none‐formate. To motivate the researchers in this area, some promising topics that have not yet been fully explored in perovskite multiferroic MOFs are finally proposed.