Circularly polarized emission

Scheme 2 is the simplest but not the only reaction scheme conceivable. The deactivation of, say, S may proceed via an excimer (SS) or a diastereomeric exciplex (SR). The same deactivation pattern holds, of course, for R, so that the deactivation in toto is nonasymmetric. If there were exciplex emission, circularly polarized fluorescence might be observed. Inoue discusses also a hot ground state path of deactivation [37]. 

Photoluminescence (PL) in the polysilanes is well documented,34b,34c and for the poly(diarylsilane)s occurs typically with a small Stokes shift and almost mirror image profile of the UV absorption.59 This is due to the similarity of the chromophore and fluorophore structures in the ground and excited states, respectively, which is a result of the fact that little structural change occurs on excitation of the electrons from the a to the a orbitals. As PL is the emissive counterpart to UV, the emissive counterpart to CD is circularly polarized pho-toluminescence (CPPL). Where the fluorophore is chiral, then the photoexcited state can return to the ground state with emission of circularly polarized light, the direction of polarization of which depends on the relative intensities of the right-handed and left-handed emissions (/R and /l, respectively), which in turn depends on the chirality of the material, or more accurately, the chirality... 

M Voigt, M Chambers, and M Grell, Circularly polarized emission from a narrow bandwidth dye doped into a chiral nematic liquid crystal, Liq. Cryst., 29 653-656, 2002. 

Developments in instrumentation have allowed measurements of the single-crystal CD spectra of [(+ )D-Cr(en)3]3+ doped in [Ir(en)3]Cl3 between 7 and 293 K. Transitions to the excited states 4T2, 47i, ZE, 27i and 2T2 were observed.418 The discussion refers to much earlier work. The polarized electronic spectra of single crystals of several trans-Cr [XY(en)2] complexes have been assigned and ligand field parameters evaluated.419 CD, absorption and circularly polarized emission spectra have been reported for [Cr(en)3]3+ in the region of the A2g 2EgTig transitions.420... 

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 optically active 1,2-dioxetane of 2,4-adamantanedione (89) was synthesized. Thermal activation of 89 yielded chemiluminescence (Xmax = 420 nm characteristic of ketone fluorescence), pointing to intermediate 90 which is chiral only in its excited state due to the out-of-plane geometry of one of the two carbonyl groups. However, circular polarization of chemiluminescence measurement of 90 has not detected optical activity at the moment of emission. The authors have concluded that fast, relative to the lifetime of ketone singlet excited state, intramolecular n, it energy transfer caused racemization of 90196. 

In circularly polarized luminescence spectroscopy, one normally reports the ratio of Al to the total intensity 7. The results are most often reported in terms of the luminescence dissymmetry ratio, glum, which is defined as the ratio of the differential emission intensity to the average total emission intensity.75... 

Most of the time-resolved emission spectroscopy setups are home made in the sense that they are built from individual devices (laser, detection system,. ..) hence they are not of a plug and press type, so that their exact characteristics may vary from one installation to the other. Some of these differences have no impact on the overall capabilities of the system but some have a drastic influence on the way the collected data are processed and analysed. This aspect will be detailed in the next section, while this section deals with a general description of the apparatus. The most basic type of apparatus will be described, with no reference to sophisticated techniques such as Time Correlated Single Photon Counting or Circularly Polarized Luminescence devices. 

Circularly polarized luminescence (CPL) from chiral molecular systems is the emission analog of circular dichroism (CD) and as such reflects the chirality of the excited state in the same maimer as CD probes reflect the chirality of the ground state (Riehl and Muller, 2005). For lanthanide ions, laige CPL (and/or CD) signals are expected for f-f transitions obeying magnetic dipole selection rules, in particular A J = 0, 1 Eu(5Do —> 7Fi), Tb(5D4 7F4, 5D4 7F5), Dy(4F9/2 6Hn/2), Yb(2Fs/2 2F7/2) emissions are typical examples. Recent... 

Analogous g-values may be defined for the degree of circular polarization in emission [or circularly polarized photoluminescence (CPPL)] and circularly polarized electroluminescence (CPEL), eg. gCppL = 2(JL - 1R)/(1L + 1r), where IL and IR denote the intensity of left- and right-handed circularly polarized emission, respectively. CPPL should not be confused with fluorescence-detected CD. 

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