Polyelectrolyte multilayers with perfluorinated phthalocyanine selectively entrapped inside the perfluorinated nanocompartments

Abstract

A novel perfluorinated magnesium phthalocyanine (MgPcF64) was synthesized and employed to probe nanodomains in hydrophobically modified, amphiphilic cationic polyelectrolytes bearing alkyl and/or fluoroalkyl side chains. MgPcF64 was found to be solubilized exclusively in the aqueous solutions of the fluorocarbon modified polycations, occupying the perfluorinated nanocompartments provided, while analogous polyelectrolytes with alkyl side chains forming hydrocarbon nanocompartments could not host the MgPcF64 dye. Multilayer films were fabricated by means of the layer-by-layer (LbL) deposition method using sodium poly(styrene sulfonate) as a polyanion. Linear multilayer growth was confirmed by UV-Vis spectroscopy and spectroscopic ellipsometry. Atomic force microscopy studies indicated that the micellar conformation of the polycations is preserved in the multilayer films. Fluorescence spectroscopy measurements confirmed that MgPcF64 stays embedded inside the fluorocarbon domains after the deposition process. This facile way of selectively incorporating water-insoluble, photoactive molecules into the structure of polyelectrolyte multilayers may be utilized for nanoengineering of ultrathin film-based optoelectronic devices.

Near Infrared Phosphorescent, Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

“…The formation of palladium 4,p latinum 5,a nd metal-free 6 perfluoro-phthalocyanines was corroborated by measuring 19 FNMR spectra in deuterated acetone. As anticipated, three resonance signals were detected for 4, 5,a nd 6.T he chemical shifts for all compounds studied were very alike, notwithstanding the presence or absence of metal in the perfluoro-phthalocyanine.…”

“…Final purification was achieved by crystallization of the materials from EtOAc. The 19 FNMR spectroscopic analysisi ndicated that both metal complexes were free from any impurities. Duringt he optimization of the reaction conditions, several metal sources, such as palladium(II) chloride, palladium(II) acetate, palladium(II) acetylacetonate, bis(triphenylphosphine)palladium(II)d ichloride, platinum(II) chloride, and platinum(II) acetylacetonate were tested.…”

“…So far,m etals such as Zn II ,C o II ,Mg II ,Fe II ,Ru II ,V = O, Tb, and Lu have been successfully incorporated into the PcF 64 scaffold. [16][17][18][19][20][21][22] The three-step procedure leadingt oc ompounds PdPcF 64 4 and PtPcF 64 5 is presented in Scheme1.S ynthesis of palladium(II) and platinum(II) complexes 4 and 5 started with the synthesis of perfluoro(4,5-diisopropyl)phthalonitrile (2)b ased on ap reviously described procedure. [23] Treatmento f am ethanolic solution of 2 with ammonia gas at room temperature afforded 1,3-diiminoisoindoline 3 in quantitative yield.…”

“…The synthesis of 4 and 5 was carriedo ut by reacting 1,3-diiminoisoindoline 3 with either PdCl 2 or PtCl 2 in nitrobenzene at 200 8Cf or 4 and at 240 8Cf or 5 in am icrowave reactor.U pon cooling the reaction mixture, phthalocyanines 4 and 5 precipitated from the nitrobenzene.P urification of 4 and 5 was achieved by washing the precipitate with different solvents followed by column chromatography on silica gel. By using this purification procedure, we successfully removeda ll but one impurity that wasi dentified by 19 FNMR spectroscopica nalysis. Final purification was achieved by crystallization of the materials from EtOAc.…”

“…d = À103 ppm. All signals were seen as multiplets because of 19 F- 19 Fc oupling. To ensure the integrity of the materials obtained,M ALDIm ass spectra of 4, 5,a nd 6 were recorded.…”