We present studies of fluorescence photomodulation and solvatochromism in nanoparticles of the conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) doped with a photochromic spirooxazine dye. The fluorescence properties of doped nanoparticles with dyes in the spirooxazine form are identical to those in undoped control nanoparticles. UV irradiation converts some of the dyes to their visibleabsorbing merocyanine form, which is an efficient quencher of MEH-PPV fluorescence. The fluorescence intensity of the nanoparticles drops to less than 10% of its initial value and recovers when the merocyanines undergo thermal reversion to spirooxazines. The fluorescence modulation can be cycled many times without fatigue or photodegradation, and the degree of quenching is linear with merocyanine concentration. The photochromic conversion can also be used as a probe of the environment within the nanoparticles as both the kinetics of the thermal merocyanine-to-spirooxazine conversion and the merocyanine absorption spectrum are sensitive to the dye environment. The kinetics of the thermal dye reversion in the nanoparticles are first order and nearly as fast as those in THF, while those in a MEH-PPV film are biexponential and substantially slower. The position of the merocyanine absorption within the nanoparticles is likewise distinct from that in a MEH-PPV film and implies a liquid-like environment that is more polar than THF. We hypothesize that those dyes that undergo spirooxazine-to-merocyanine conversion are adhered to solution-exposed MEH-PPV segments within the nanoparticles or to the particle surface and thus have ample free volume for the photochromic conversion. These findings will be useful in designing future stimulus-responsive nanoparticle systems.
Binding of a porphyrin carboxylate anion () to tetrathiafulvalene calix[4]pyrrole (TTF-C4P) results in electron transfer from TTF-C4P to Li(+)@C60 to produce the charge-separated state (1/TTF-C4P˙(+)/Li(+)@C60˙(-)) in benzonitrile. Upon photoexcitation of , photoinduced electron transfer from the triplet excited state of to TTF-C4P˙(+) occurs to produce the higher energy charge-separated state (˙(+)/TTF-C4P/Li(+)@C60˙(-)), which decays to the ground state with a lifetime of 4.8 μs.
The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F(-), Cl(-), and Br(-)) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.
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