Lanthanide complexes circularly polarized emission

A further variation on the theme of emission is circularly polarized emission, where chiral interactions, for example between a lanthanide complex and a chiral ligand in solution, can be studied. Selection rules have been given619 based on S, L and / values for 4/states perturbed by spin-orbit coupling and 4/ electron-crystal field interactions, and four types of transition were predicted to be highly active chiroptically. These are given in Table 12. 

The interaction of aspartic acid and other ligands with complexes of Tb " with edta and related ligands has also been studied and association constants determined. The complex formation between Tb " or Eu " and (r)-( — )-l,2-propanediaminetetraacetic add or (r,r)-trons-1,2-cyclohexanediaminetetraacetic acid has been similarly investigated. The pH dependence of the circularly polarized and total luminescence shows a drastic configurational change of the chelate system at pH 10.5-11, corresponding, it is believed, to formation of hydroxide complexes. Tlie technique of magnetic-field-induced circularly polarized emission has been introduced for lanthanide ions the mechanisms of lanthanide transition intensities are also discussed in the paper. 

The first two chapters of this work cover theoretical and practical aspects of the emission process, the spectroscopic techniques and the equipment used to characterize the emission. Chapter 3 introduces and reviews the property of circularly polarized emission, while Chapter 4 reviews the use of lanthanide ion complexes in bioimaging and fluorescence microscopy. Chapter 5 covers the phenomenon of two-photon absorption, its theory as well as applications in imaging, while Chapter 6 reviews the use of lanthanide ions as chemo-sensors. Chapter 7 introduces the basic principles of nanoparticle upconversion luminescence and its use for bioimaging and Chapter 8 reviews direct excitation of the lanthanide ions and the use of the excitation spectra to probe the metal ion s coordination environment in eoordination compounds and biopolymers. Finally, Chapter 9 describes the formation of heterobimetallic complexes, in whieh the lanthanide ion emission is promoted through the hetero-metal. 

This analysis was made possible by our ability to measure CPL from racemic solutions of lanthanide complexes through use of circularly polarized excitation [12,45-47]. The varied lifetime of the lanthanide (III) ions allow for some insight concerning the lability of complexes of this type. For example, we have shown that although no CPL is detected in the luminescence from tris-terdentate complexes of Tb(III) and Eu(III) with oxydiacetate (ODA), CPL is observed from DytDPA -, indicating that, indeed, this complex is D3 in aqueous solution, but that only for the short lived Dy(III) ion (x = 20 psec) is the photoprepared enantiomerically-enriched excited state maintained throughout the emission lifetime [45]. 

A number of lanthanide complexes have been shown to exhibit circularly polarized luminescence (CPL—the differential spontaneous emission of left- and right-circularly polarized light). In the absence of any externally applied fields, CPL is exhibited only by systems that have net chirality in their structures or are subject to chiral perturbations by their environment. CPL exhibited by the Af-Af transitions of chiral lanthanide systems provides a sensitive probe of coordination and structure in solution. Applications are limited to systems which possess some element of chirality, but in many cases this merely requires that > 1 ligand of interest has a chiral atom or carries a chiral label (such as a chiral substituent group). ... 

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