Complementarity and Preorganization

Abstract

The principle of complementarity states that “to complex, hosts must have binding sites which can simultaneously contact and attract the binding sites of the guests without generating internal strains or strong nonbonded repulsions.” The principle of preorganization states that “the more highly hosts and guests are organized for binding and low solvation prior to their complexation, the more stable will be their complexes.” This chapter presents examples of classical and contemporary systems that exemplify different aspects of these two principles which are cornerstones of the discipline of supramolecular chemistry. The final sections of the chapter discuss situations (e.g., chemical sensing arrays and dynamic combinatorial chemistry) where adhering to the principle of preorganization may be detrimental to the function of the system.

Recent progress in development of 2,3-diaminomaleonitrile (DAMN) based chemosensors for sensing of ionic and reactive oxygen species

“…The signicant changes in emission and absorption spectrum upon addition of uoride was explained on the basis of hydrogen bond interaction between F À ion and N-H group of indole moiety. The sensing studies of chemosensor (5) has been validated by 1 H NMR titration and spectrophotometric titrations. Apart from DAMN based organic molecules, DAMN based metal complexes also showed interesting sensing properties.…”

“…[1][2][3] Sensor molecules derived from these concepts have a suitable orientation of functional groups which produce strong covalent and non-covalent interactions between sensors and target guest species. [4][5][6] Different scaffolds like calixarenes, cyclotriveratrylene, cyclodextrin, borondipyrromethene (BODIPY), naphthalimides, crown-ethers/thiacrown-ethers, resorcinarenes etc. were successfully used for designing chemosensor molecules for sensing of specic ions and neutral species.…”

Multivalent and Photoresponsive Assembly of Dual‐Cavity Baskets in Water

“…These stable (i.e., not leaking the basket or guest molecules into the external solution through dialysis, see Figures S9 and S10) and, apparently, well‐structured materials hold fluorescent dye molecules in their reservoirs and can be photo‐switched from one form into another, albeit with some loss of the molecular cargo. A multitude of host–guest contacts along with complementarity could, in future, play an essential role in designing photo‐switchable materials and devices for a variety of applications, from programmable drug‐delivery formulations to nanoreactors.…”

“…Am ultitudeo fh ost-guest contacts [24] along with complementarity [29] could, in future, playa ne ssential role in designing photo-switchable materials and devicesf or av ariety of applications, from programmabledrug-delivery formulationst o nanoreactors. Am ultitudeo fh ost-guest contacts [24] along with complementarity [29] could, in future, playa ne ssential role in designing photo-switchable materials and devicesf or av ariety of applications, from programmabledrug-delivery formulationst o nanoreactors.…”

Elucidating the 3D structures of Al(iii)–Aβ complexes: a template free strategy based on the pre-organization hypothesis

“…This concept is recurrent in many molecular fields nowadays from protein–ligand interactions ( i.e. in the conformational selection hypothesis), 32 , 33 de novo enzyme design, 34 – 36 metal binding to proteins, 37 cyclic peptides, 38 supramolecular chemistry, 39 and inorganic chemistry especially when dealing with multidentate ligands. 40 , 41 Although the exact contributions of pre-organization and induced effects in the binding processes are not yet clear – likely depending on the system under investigation – the former offers a possible solution to the absence of a structural template for the Al( iii )–Aβ system.…”