Ionic liquids have attracted a great deal of interest in recent years, illustrated by their applications in a variety of areas involved with chemistry, physics, biology, and engineering. Usually, the stabilities of ionic liquids are highlighted as one of their outstanding advantages. However, are ionic liquids really stable in all cases? This review covers the chemical stabilities of ionic liquids. It focuses on the reactivity of the most popular imidazolium ionic liquids at structural positions, including C2 position, N1 and N3 positions, and C4 and C5 positions, and decomposition on the imidazolium ring. Additionally, we discuss decomposition of quaternary ammonium and phosphonium ionic liquids and hydrolysis and nucleophilic reactions of anions of ionic liquids. The review aims to arouse caution on potential decomposition of ionic liquids and provides a guide for better utilization of ionic liquids.

Research on ionic liquids has achieved rapid progress in the last several decades. Stability is a prerequisite for the application of ionic liquids. Ionic liquids may be used at elevated temperature, as electrolytes, or under irradiation. Therefore, the thermal, electrochemical, and radiolytic stabilities of ionic liquids are important and need to be known before their usage. Many research papers and some reviews on the stabilities of ionic liquids have been published. However, new results are continuously being published and a comprehensive review and perspective on this topic are still urgently needed. In this perspective, we intend to provide a comprehensive review including characterization methods, the effects of chemical composition of the ionic liquids on the thermal, electrochemical, and radiolytic stabilities of ionic liquids, respectively. Moreover, the thermal stability of some special types of ionic liquids such as poly(ionic liquids) and mixed ionic liquids, and the thermal and electrochemical stabilities of protic ionic liquids are discussed too. For thermal stability, the interactions between ions are less important than the individual anions and cations. The decomposition temperature is mainly determined by the less-stable ion, usually the anion. For electrochemical stability, the electrochemical window is determined by both the cation and anion. The less stable ion could influence the stability by interaction between the generated species from the decomposition with the more stable ion (opposite ion). This perspective is helpful for people to avoid using unstable ionic liquids and choose suitable ionic liquids.

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Homogeneous catalysts generally show higher catalytic activities, while heterogeneous catalysts are more easily separated from products. To combine the advantages of heterogeneous and homogeneous catalysts has been of great interest for many years. Here, we report a kind of facilely prepared cross-linked poly­(ionic liquid)­s (PILs) with swelling property to increase catalytic activities of heterogeneous catalysts. The swelling ability of PILs was greatly affected by cross-linking density and chain length of substituents on imidazolium, and the unique swelling property prompted the nonporous PILs to contact with substrates sufficiently, enhancing their catalytic activities similar to homogeneous ionic liquid monomers.

An effective one‐pot method for the conversion of carbon dioxide, ethylene oxide, and amines to 3‐aryl‐2‐oxazolidinones has been developed. This one‐pot method consists of two parallel reactions and a subsequent cascade reaction between the two products of the corresponding parallel reactions. Notably, the binary ionic liquids of 1‐butyl‐3‐methyl‐imidazolium bromide and 1‐butyl‐3‐methyl‐imidazolium acetate demonstrate a synergistic catalytic effect on this new strategy. 1‐Butyl‐3‐methyl‐imidazolium bromide is essential in two parallel reactions owing to the good nucleophilicity and leaving ability of bromide, and 1‐butyl‐3‐methyl‐imidazolium acetate plays a dominant role in the subsequent cascade reaction owing to the strong basicity of acetate. In addition, the binary ionic liquids can be used thrice without significant loss of catalytic activity.

The cooperative effects of cation–anion are elucidated in ionic liquid‐catalyzed reactions of aniline with ethylene carbonate and the reaction of phenylacetonitrile with dimethyl carbonate. Cations of ionic liquids activate electrophiles by the proton in the 2‐position of the imidazolium ring through the hydrogen‐bond interaction with the carbonyl group. The catalytic activity follows the order of 1‐butyl‐3‐methyl‐imidazolium ([Bmim])>1,2‐dimethyl‐3‐butyl imidazolium ([Bmmim])>1‐butyl‐pyridinium ([Bpy]), which is consistent with the order of the hydrogen bond donor ability. Simultaneously, anions of ionic liquids activate nucleophiles by accepting the hydrogen bond. The catalytic activity of imidazolium‐based ionic liquids follows the order Cl>Br>BF4>PF6>C(CN)2COOEt≈NTf2>BPh4, which is consistent with the order of the hydrogen bond acceptor ability. The dual activation of nucleophiles and electrophiles by the cations and anions of ionic liquids is crucial to promote the reaction in high yields.

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An oxido-vanadium(V) site encapsulated in a highly confined space of molecular cage displays enzyme-like catalytic behaviour.