Cation and anion recognition have both played central roles in the development of supramolecular chemistry. Much of the associated research has focused on the development of receptors for individual cations or anions, as well as their applications in different areas. Rarely is complexation of the counterions considered. In contrast, ion pair recognition chemistry, emerging from cation and anion coordination chemistry, is a specific research field where co-complexation of both anions and cations, so-called ion pairs, is the center of focus. Systems used for the purpose, known as ion pair receptors, are typically di-or polytopic hosts that contain recognition sites for both cations and anions and which permit the concurrent binding of multiple ions. The field of ion pair recognition has blossomed during the past decades. Several smaller reviews on the topic were published roughly 5 years ago. They provided a summary of synthetic progress and detailed the various limiting ion recognition modes displayed by both acyclic and macrocyclic ion pair receptors known at the time. The present review is designed to provide a comprehensive and up-to-date overview of the chemistry of macrocycle-based ion pair receptors. We specifically focus on the relationship between structure and ion pair recognition, as well as applications of ion pair receptors in sensor development, cation and anion extraction, ion transport, and logic gate construction. CONTENTS 3.4.
Conjugated polymers have emerged as promising candidates for photocatalytic H2 production owing to their structural designability and functional diversity. However, the fast recombination of photoexcited electrons and holes limits their H2 production rates. We have now designed molecular heterostructures of covalent triazine frameworks to facilitate charge‐carrier separation and promote photocatalytic H2 production. Benzothiadiazole and thiophene moieties were selectively incorporated into the covalent triazine frameworks as electron‐withdrawing and electron‐donating units, respectively, by a sequential polymerization strategy. The resulting hybrids exhibited much improved charge‐carrier‐separation efficiency as evidenced by photophysical and electrochemical characterization. An H2 evolution rate of 6.6 mmol g−1 h−1 was measured for the optimal sample under visible‐light irradiation (λ>420 nm), which is far superior to that of most reported conjugated‐polymer photocatalysts.
Two or more anions constrained in close proximity within a single pocket are found in a number of natural systems but a less common motif in artificial systems. This review summarizes work on anion receptors capable of stabilizing anionic dimers, trimers, tetramers and clusters in a well-defined fashion. These systems may provide insights into the fundamental chemistry of anion-anion interactions and provide a guide for understanding in greater detail a number of biological and environmental processes, as well as key tenants of relevance to supramolecular chemistry, extraction, transport, crystal engineering, and the like. The primary goal of this review is to provide a general introduction into multi-anion recognition chemistry for the benefit of supramolecular and non-supramolecular chemists alike.
Supramolecular chemistry is a central topic in modern chemistry.
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