Excimers dendrimers

In order to study the molecular dynamics of the outer segments of a dendrimer, one pyrene moiety was selectively and covalently attached to one dendron of poly(aryl ester) dendrimers by Adams (in total three pyrene molecules per dendrimer) [24]. The fluorescence decay of pyrene in the THF solution of the labeled dendrimers provided details of the pyrene excimer formation, such as the excimer formation rate, the excimer decomposition rate constant and the equilibrium constant of the excimer formation. These parameters were utilized to evaluate the diffusional mobility of the dendrimer branches. 

In acetonitrile-dichloromethane 1 1 v/v solution, their absorption spectra are dominated by naphthalene absorption bands and they exhibit three types of emission bands, assigned to naphthyl localized excited states (/Wx = 337 nm), naphthyl excimers (Amax ca. 390 nm), and naphthyl-amine exciplexes (/lmax = 480 nm) (solid lines in Fig. 3). The tetraamine cyclam core undergoes only two protonation reactions, which not only prevent exciplex formation for electronic reasons but also cause strong nuclear rearrangements in the cyclam structure which affect excimer formation between the peripheral naphthyl units of the dendrimers. 

A first generation poly(amido amine) dendrimer has been functionalized with three calyx[4]arenes, each carrying a pyrene fluorophore (4) [30]. In acetonitrile solution the emission spectrum shows both the monomer and the excimer emission band, typical of the pyrene chromophore. Upon addition of Al3+ as perchlorate salt, a decrease in the excimer emission and a consequent revival of the monomer emission is observed. This can be interpreted as a change in the dendrimer structure and flexibility upon metal ion complexation that inhibits close proximity of pyrenyl units, thus decreasing the excimer formation probability. 1H NMR studies of dendrimer 4 revealed marked differences upon Al3+ addition only in the chemical shifts of the CH2 protons linked to the central amine group, demonstrating that the metal ion is coordinated by the dendrimer core. MALDI-TOF experiments gave evidence of a 1 1 complex. Similar results have been obtained for In3+, while other cations such as Ag+, Cd2+, and Zn2+ do not affect the luminescence properties of... 

The energy dissipation in the dendrimer bearing a certain number of pery-lenemonoimide chromophores can be followed by applying time resolved fluorescence techniques. These measurements indicate excimer-like interactions among neighboring perylenemonoimide dyes. Furthermore, two types of motion are detected a rotation of the whole molecule and a fractional motion maybe of the dendrimer branch [68]. 

The stilbene carbon unit has also been peripherally bound to POPAM cores. Although it does not strictly belong to the hydrocarbon dendrimers, the formula of a G2 dendrimer of this type (Fig. 4.21) is depicted here as an example. It was obtained by alkylation of the corresponding eightfold mono-sulphonamide with 4-(bromomethyl)stilbene. Its fluorescence, E/Z isomerisation, photoisomerisation (see Section 5.2.2), and excimer formation were compared with those of non-dendritic stilbenes. The quantum yields of photoisomerisation (0.30) and fluorescence of the E isomer (0.014) of the dendrimer proved to be substantially lower [38]. 

In acetonitrile/dichloromethane solution this type of dendrimer shows three kinds of emission bands having their origin in the excited state localised within the naphthyl group, a naphthyl excimer, and a naphthyl/amine exciplex. Titration with trifluoroacetic acid revealed that, in spite of formally possessing four nitrogen atoms, the cyclam core undergoes only two successive protonation steps which significantly affect the luminescence properties. 

The protonated dendrimer exhibits a far more intense excimer band than corresponding Frechet dendrons without a cyclam core. One possible reason for this behaviour is that excimer formation is facilitated by folding of the - flexible - benzyl ether framework. Whereas a change in emission intensity is observed in the course of protonation of the cyclam dendrimer, a reference substance containing no cyclam and benzene moieties (Fig. 5.17) shows a linear increase... 

The non-linear spectral changes of the naphthyl-localised exciplex and exci-mer bands occur after addition of the first two equivalents of trifluoroacetic acid. It is thus unnecessary to protonate all of the nitrogen atoms in order to suppress exciplex formation since - expressed figuratively - the nitrogen atoms share the protons. Moreover, protonation not only provides protection against exciplex formation but also leads to conformational changes in the cyclam unit itself, which in turn affects excimer formation between peripheral naphthyl units of the dendrimer. 

These results indicate that in the individual dendrimers, interactions take place both in the ground state and in the excited state between the naphthyl units and also between naphthyl and amine units of the dendrimer branches which result in dimer/excimer and charge-transfer/exciplex excited states. 

Incomplete coverage of the surface of such a fifth-generation POPAM dendrimer exposes hydrophobic areas of adamantyl units remaining uncomplexed by cyclodextrins on the dendritic outer shell [38]. Pyrenes were used as neutral fluorescence probes to examine whether this might lead to aggregation in water driven by the hydrophobic effect [39a]. Their inclusion in the dendrimer/cyclo-dextrin aggregate leads to changes in fluorescence intensity and in the vibrational fine structure. Formation of excimers was also observed. 

Fig. 4. Schematic (a) representation of excimer and exciplex formation in a dendrimer and (b) energy level diagram showing the three types of emissions that can result.

A step further in cyclam-based dendritic ligands for metal ions is constituted by dendrimer 6 (Fig. 13), containing two covalently linked cyclam units as a core, appended to six branches, each one of them consisting of a dimethoxybenzene and two naphthyl units 38). Its photophysical properties are qualitatively similar to that observed for 5. For example, the emission spectrum evidences the presence of naphthyl-localized excited states ( max = 337 run), naphthyl excimers Umax ca. 390 nm), and naphthyl-amine exciplexes (lmax = 480 nm). 

From the small difference in the spectral width (vide supra), the assumption of an excited state excimer-like (or dimer) chromophore-chromophore interaction is possible but not conclusive. Better insight into the extent of excimer-like emission is obtained from the fluorescence decays, where only for the multichromophoric dendrimers is a long decay component of 7.4 ns observed along... 

In addition to the antennae effect, dendrimers are also effective insulators and exhibit the shell effect. In providing a dense shell around the incorporated chromophores, dendrimers effectively prevent aggregation which leads to non-emissive excimers and self-quenching that occurs when chromophores with small Stokes shifts are within short distances of one another. This shell effect allows for increased photoluminescence efficiency of the enclosed chromophore, which is important for optoelectronic devices. 

Exitation wavelength, nm Dendrimer generation Excimer/ monomer ratio... 

As the evolution of the red-tail aggregate or excimer emission occurs on much longer timescales than the spectral red-shift due to energy transfer, the rapidly relaxed dendrimer core spectrum (i. e. the spectrum in Fig. 8.7 taken at 100 ps delay) can be taken as the emission arising from the lowest-energy conformation of the molecules within their disorder broadened density of states. Subtracting this lowest-order electronic emission from subsequent emission spectra yields the pure intermolecular spectral component, as shown in the inset of Fig. 8.8. The rise and decay of the excitonic and intermolecular emission can be clearly resolved using this technique, which demonstrates directly the tendency for pheny-lene-vinylene units to form intermolecular excited state species [116]. Rather than... 

There are a number of studies on pyrene labelled or doped polymer materials. Dendritic size and electrostatic forces in poly(amido) dendrimers with pyrene residues have been determined through the use of a variety of quenchers. As the dendritic size increases so the Stern-Volmer quenching constant decreases, owing to blocking of the pyrene chromophore by the growing dendritic network. The photophysical properties of poly(acrylic acids) tagged with pyrene has been measured in micellar media at various pHs." The ratio of monomer to excimer gave valuable information on the micropolarity sensed by the pyrene label, as well as the influence of external stimuli. The surfactant... 

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