Antenna effect luminescence

Luminescence experiments in dichloromethane solution indicated that the fluorescence of the phenylacetylene branches is quenched, whereas intense emission is observed from the binaphthol core. This antenna effect represents the first example of efficient (>99%) energy migration in an optically pure dendrimer. The fluorescence quantum yield increases slightly with increasing generation the values of 0.30,0.32, and 0.40 were obtained, respectively, for 10-12. 

Antenna Effects of Aromatic Dendrons and Their Luminescence Applications... 

The morphological dependence of the antenna effect was quantitatively studied by the comparison of the three focal isomers of benzene-cored 4th-genera-tion dendrimers [7]. The energy of the photon absorbed by the dendron subunits must be dissipated either through radiative (luminescence) or nonradia-... 

Self-assembly of aromatic dendron subunits has been tried by the design of coordination to multivalent metal cations (i.e., metal-cored dendrimer complexes). Several metal-cored dendrimer complexes have successfully exhibited luminescence by antenna effects. 

A supramolecular assembly of macromolecules bearing antenna dendron has been reported. Pyrazole-anchored PBE dendrons were synthesized to examine the coordination behavior to transition-metal cations (Cu, Au, Ag) [31]. Self-assembled metallacycles were found. The Cu-metallacycle further formed luminescent fibers about 1 pm in diameter. The luminescence (605 nm) occurred by the excitation of the dendron (280 nm) and the excitation spectrum was coincident with the absorption spectrum of the dendron, suggesting the antenna effect. Interestingly, the luminescence of the Cu-metallacycle fiber disappeared when the fiber was dissociated into the individual metallacycles in C2H2. 

Kawa, M., and Frechet, J.M.J. (1998) Self-assembled lanthanide-cored dendrimer complexes enhancement of the luminescence properties of lanthanide ions through site-isolation and antenna effects. Chem. Mater. 10, 286-296. 

Kawa M, Takahagi T (2004) Improved antenna effect of terbium(III)-cored dendrimer complex and green-luminescent hydrogel by radical copolymerization. Chem Mater 16 2282-2286... 

The mechanism for sensitized luminescence using the antenna effect is shown schematically in Fig. 2. 

Alpha, B. Ballardini, R. Balzani, V. Lehn, J.-M. Perathoner, S. Sabbatini, N. Antenna effect in luminescent lanthanide cryptates a photophysical study. Photochem. Photobiol. 1990, 52(2), 299—306. 

When looking for R(III) determination, use can be made of the antenna effect already discussed in sect. 3.7, provided the lanthanide of interest is luminescent. The basic principle is to add a given organic ligand, which will ensure a high complexation constant with the lanthanide together with an efficient UV absorption and energy transfer to the R(III)... 

As it is well known, sensitization of Ln-centered luminescence can be achieved via an intramolecular energy transfer upon excitation of organic ligands, instead of using direct excitation of the weak Lnm absorption bands. This phenomenon now called antenna effect or luminescence sensitization has first been observed in 1942 by Weissman for europium(III) complexes formed with salicylaldehyde and with /3-diketonates, more particularly benzoyl-acetonate (ba, 48a), dibenzoylmethanate (dbm, 48b) and wieta-nitrobenzoylacctonatc (47a, fig. 41) (Weissman, 1942). 

Kawa M. Antenna effects of aromatic dendrons and their luminescence applications. Top Curr Chem 2003 228 193-204. 

Since the dipole strength of/-/ transitions are formally forbidden, typically, these extinction coefficients are of the order of 1 M cm an alternative path has to be used which is called luminescence sensitization or antenna effect, that is when the luminescent ion is coordinated with an organic ligand or imbedded into a matrix, then the energy absorbed will be transferred from the surrounding onto the luminescent ion and subsequently the ion emits characteristic light. 

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