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II. Using Fluoro/Lumophores for Signaling: The advantages of molecular fluorescence or lumi- nescence for sensing and switching can be sum- marized;7,8 high sensitivity of detection down to the single molecule,38a,40-44 “on-off” switchability, feasi- bility of human-molecule communication, subnan- ometer spatial resolution with submicron visuali- zation34-38 and submillisecond temporal resolution. Furthermore, many of the structural features which control (reduce) fluorescence efficiency have been delineated;45-51 double-bond torsion, low energy nπ* levels, “heavy” atoms, weak bonds, and opportunities for photoinduced electron transfer (PET) or electronic energy transfer (EET). The importance of extensive delocalization in compensating for these negative effects has also been appreciated. Therefore, consid- erable opportunities exist for modulating these struc- tural features via chemical or physical means at the molecular level. Our emphasis will be on the transduction of discrete and stoichiometric recognition events into fluorescence signals. However, nonstoichiometric interactions such as solvation have much to teach us in this field. In fact, it will become clear that the information gleaned from the fluorescence effects due to nonstoichiomeric interactions is not only important in its own right. Such data can be adapted, some- times rather directly, by designers of molecular and atomic recognition systems. The plan of the review is as follows. First, we consider emissive photophysical effects arising from monofluoro/lumophore components. Additional com- ponents if present will only serve in auxiliary capaci- ties. The supramolecular aspects will mainly arise from the necessary interaction of the environment or guest with the fluoro/lumophore. Most of the prin- cipal types of excited states encountered by organic and inorganic chemists will be represented in sec- tions III-VII. From then on, the photophysical phe- nomena themselves take on a supramolecular char- acter, i.e. two or more components are essential for the phenomenon. Their perturbation by the environ- ment/guest will form the second layer of supramolecu- larity. One of these phenomena, photoinduced elec- tron transfer (PET) can occur in monofluoro/lumophore systems (section VIII). Others require multi- fluorophore assemblies for their operation. Monomer/ excimer equilibria and electronic energy transfer (EET) are taken up in sections IX and X, respectively. |
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