Excimer-based cation sensors

When a fluoroionophore contains two fluorophores whose mutual distance is affected by cation complexation, recognition of this cation can be monitored by the monomer/excimer fluorescence-intensity ratio (see Chapter 4, Section 4.4.1 for ex-rimer formation). Cation binding may favor or hinder exrimer formation. In any case, such a ratiometric method allowing self-calibration measurement is of great interest for practical applications. 

Box 10.2 Calixarene-based fluorescent molecular sensors for sodium ions 

Such an enhancement of the fluorescence quantum yield can be explained in terms of the relative locations of the singlet n-n and n-n states. In the absence of cation the lowest excited states has n-n character, which results in an efficient intersystem crossing to the triplet state and consequently a low fluorescence quantum yield. In the presence of cation, which strongly interacts with the lone pair of the carbonyl group, the n-n state is likely to be shifted to higher energy so that the lowest excited state becomes n-n. An outstanding selectivity of Na+ versus K+ was found the ratio of the stability constants is 1300 in a mixture of ethanol and water (60 40 v/v). 

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