Anion-Templated Self-Assembly: Organic Compounds


Mark R. Sambrook Inorganic Chemistry Laboratory, University of Oxford

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The field of self-assembly is an increasingly attractive area of supramolecular chemistry. With many principles derived from biological systems, it often enables the synthesis of large, complex structures that would be far too demanding using conventional covalent techniques. Utilizing weak, reversible, noncovalent interactions, self-assembly can, through rational design of simple ligands, help minimize the amount of information inherent in the building blocks for the system and allow for error checking and self-correction. To date, the range of noncovalent interactions used in self-assembly processes includes hydrogen bonding, metal coordination, hydrophobic, and π–π donor–acceptor interactions. The range of structures prepared via templated self-assembly continues to become increasingly diverse and intricate.

Interest in the binding and recognition of anionic guest species has increasingly grown in the last decade or so, such that the field is now considered an important area of supramolecular chemistry. Anions often play key roles in biological processes; many enzyme substrates and cofactors are anionic and DNA itself is a polyanion. The fields of medicine and catalysis also help illustrate the diverse areas in which anions play key roles. Some anions are of environmental concern (e.g., there is a need to sense and remove nitrate and phosphate pollutants from natural waterways). In the past two decades, progress in the binding and recognition of anions has advanced considerably, and there are now many reviews dedicated entirely to this specific area of supramolecular chemistry.

In light of this, it is surprising that investigations into the use of anions as templates in the self-assembly of supramolecular architectures has, until recently, been limited. Reasons for this may stem from the anion's small charge-to-radius ratio (more diffuse nature), pH sensitivity, and high solvation energy. The large geometrical diversity found in anions indicates the possibilities for predefining a wide range of supramolecular structures.

At the time of writing, we are unaware of any reviews dedicated solely to anion-templated self-assembly and are thus led to believe that this encyclopedia offers the first reviews of this topic.a

aSince the submission of this review article, Ref. has appeared in the literature.

Readers interested in anion-templated self-assembly of inorganic based frameworks are directed to the article “Anion-Templated Self-Assembly: Inorganic Compounds.” This article focuses solely on the anion-templated self-assembly of organic compounds.