Advances in Supramolecular Chemistry. Volume 4 by G.W. Gokel

By G.W. Gokel

The target in quantity four of Advances in Supramolecular Chemistry is still similar to for earlier volumes: to give a large variety of supramolecular technological know-how recorded through a global panel of distinct researchers. Contributions during this quantity span the medical diversity from digital gadget improvement to novel artificial receptor molecules to biomimetic ion channels.The actual breadth of the supramolecular chemistry box is typically neglected. by means of their very nature, targeted monographs can't span the variety of efforts that come with analytical, inorganic, natural, actual, and biochemistry. Even contemplating the big variety of reports underway, there's a few polarization among the organic part of upramolecular technological know-how and fabrics improvement. it really is was hoping that the standard of the shows during this quantity will reveal that there's unique, interesting, and perfect technological know-how on each side and through the box of supramolecular chemistry.

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The closest relation in the literature is a polydisperse polymer doubly labeled with the pH-sensitive fluorophore fluorescein and pH-insensitive rhodamine. 2~ This is neither a well-characterized small molecule nor is it based on PET designs. Besides its utility for biomonitoring, 88 also shows how the competition between PET and EET is influenced by pH. In particular, 88 acts as a triad system. Some triads have received much attention as solar energy converters. 92 EET in 88 occurs across an intervening electron pair via a "stepping stone" mechanism.

PRASANNA DE SILVA ETAL. J G Me 6O + Me 59 8. INTEGRATED LUMOPHORE-RECEPTOR SYSTEMS These systems are outside the scope of the present review for several reasons. Since the lumophore and the receptor merge almost seamlessly, they cannot be classed as supramolecular systems in a structural and compartmental sense. In fact, the only supramolecular feature is in the binding of guest ions. Mechanistically these systems cannot involve PET processes since thecomponents needed for electron transfer are not clearly distinguishable (however, see Section 7 where the components can emerge in the excited state).

In contrast to Figure 1, the direction of the electron transfer is such that the process is encouraged only when the cationic guest is bound to the receptor. Now luminescence loses the competition when cationic guests are present on/in the receptor. (b) Frontier molecular orbital diagrams corresponding to part (a). The intermolecular electron transfer is exergonic only in the cation-bound case when the LUMO' of the receptor is lower in energy than the LUMO of the lumophore. Note that the LUMO' and the HOMO' of the receptor are stabilized upon cation binding.

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