Anion recognition chemistry has grown from its beginnings in the late 1960s with positively charged ammonium cryptand receptors for halide binding to, at the end of the millennium, a plethora of charged and neutral, cyclic and acyclic, inorganic and organic supramolecular host systems for the selective complexation, detection, and separation of anionic guest species. Solvation effects and pH values have been shown to play crucial roles in the overall anion recognition process. More recent developments include exciting advances in anion-templated syntheses and directed self-assembly, ion-pair recognition, and the function of anions in supramolecular catalysis.

Anion Recognition and Sensing: The State of the Art and Future Perspectives

Fluorogenic and chromogenic chemosensors and reagents for anions.

The miniaturization of components used in the construction of working devices is being pursued currently by the large-downward (top-down) fabrication. This approach, however, which obliges solid-state physicists and electronic engineers to manipulate progressively smaller and smaller pieces of matter, has its intrinsic limitations. An alternative approach is a small-upward (bottom-up) one, starting from the smallest compositions of matter that have distinct shapes and unique properties-namely molecules. In the context of this particular challenge, chemists have been extending the concept of a macroscopic machine to the molecular level. A molecular-level machine can be defined as an assembly of a distinct number of molecular components that are designed to perform machinelike movements (output) as a result of an appropriate external stimulation (input). In common with their macroscopic counterparts, a molecular machine is characterized by 1) the kind of energy input supplied to make it work, 2) the nature of the movements of its component parts, 3) the way in which its operation can be monitored and controlled, 4) the ability to make it repeat its operation in a cyclic fashion, 5) the timescale needed to complete a full cycle of movements, and 6) the purpose of its operation. Undoubtedly, the best energy inputs to make molecular machines work are photons or electrons. Indeed, with appropriately chosen photochemically and electrochemically driven reactions, it is possible to design and synthesize molecular machines that do work. Moreover, the dramatic increase in our fundamental understanding of self-assembly and self-organizational processes in chemical synthesis has aided and abetted the construction of artificial molecular machines through the development of new methods of noncovalent synthesis and the emergence of supramolecular assistance to covalent synthesis as a uniquely powerful synthetic tool. The aim of this review is to present a unified view of the field of molecular machines by focusing on past achievements, present limitations, and future perspectives. After analyzing a few important examples of natural molecular machines, the most significant developments in the field of artificial molecular machines are highlighted. The systems reviewed include 1) chemical rotors, 2) photochemically and electrochemically induced molecular (conformational) rearrangements, and 3) chemically, photochemically, and electrochemically controllable (co-conformational) motions in interlocked molecules (catenanes and rotaxanes), as well as in coordination and supramolecular complexes, including pseudorotaxanes. Artificial molecular machines based on biomolecules and interfacing artificial molecular machines with surfaces and solid supports are amongst some of the cutting-edge topics featured in this review. The extension of the concept of a machine to the molecular level is of interest not only for the sake of basic research, but also for the growth of nanoscience and the subsequent development of nanotechnology.

Artificial Molecular Machines.

Dynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, however, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is noncovalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/1521-3773%2820020503%2941%3A9%3C1460%3A%3AAID-ANIE11111460%3E3.0.CO%3B2-N

Dynamic covalent chemistry.

Dynamic combinatorial chemistry.

Dipyrrolylquinoxalines: Efficient Sensors for Fluoride Anion in Organic Solution

The use of the 3,4-difluoro-1H-pyrrole as a building block for the preparation of octamethyloctafluorocalix[4]pyrrole and 2,3-di(3‘,4‘-difluoropyrrol-2‘yl)quinoxaline is described. These latter two entities act as neutral anion receptors and were found to bind anions such as fluoride, chloride, or dihydrogen phosphate with an enhanced affinity compared to their non-fluorinated congeners as judged from 1H NMR, 19F NMR, and fluorescence emission spectroscopic analyses. The increase in affinity was especially high in case of chloride and dihydrogen phosphate anion, with the 2,3-di(3‘,4‘-difluoropyrrol-2‘-yl)quinoxaline system, in particular, displaying an affinity for H2PO4- that was improved by 3 orders of magnitude as compared to its non-fluorinated congener. This improvement in the affinity for the dihydrogen phosphate is accompanied by change of color from pale yellow to orange, thus allowing the use of such compounds as naked-eye sensors for phosphate anion. In the case of the octafluorocalix[4]pyrrole ...

Fluorinated Calix[4]pyrrole and Dipyrrolylquinoxaline: Neutral Anion Receptors with Augmented Affinities and Enhanced Selectivities

Surface plasmon resonance analysis at a supported lipid monolayer

Resolution of the bisporphyrin Troger's base analogue 1 affords homochiral clefts that tightly bind histidine esters in 80–86% e.e. and lysine benzyl ester in 48% e.e.; the histidine esters are bound in fixed conformations that can be readily detected by 1H NMR spectroscopy as a result of the large dispersion of proton resonances by the ring currents of the two porphyrins.

Enantioselective recognition of histidine and lysine esters by porphyrin chiral clefts and detection of amino acid conformations in the bound state

2-Amino-5,10,15,20-tetraarylporphyrins react with formaldehyde to give good yields of the corresponding octaaryl derivatives of the Troger's base analogue in which two porphyrins are covalently Jinked by a diazocine bridge; the X-ray crystal-structure of the bis(tetraphenylporphyrinato)dipalladium(II) derivative 6 reveals a concave chiral cavity with two metal ion binding sites suitable for ditopic interactions with guest molecules.

Andrew C. Try

Papers

Dipyrrolylquinoxalines: Efficient Sensors for Fluoride Anion in Organic Solution

Fluorinated Calix[4]pyrrole and Dipyrrolylquinoxaline: Neutral Anion Receptors with Augmented Affinities and Enhanced Selectivities

Surface plasmon resonance analysis at a supported lipid monolayer

Enantioselective recognition of histidine and lysine esters by porphyrin chiral clefts and detection of amino acid conformations in the bound state

Porphyrin analogues of Tröger's base: Large chiral cavities with a bimetallic binding site