Group III perfluoroalkyl perfluoro phthalocyanines

Abstract

We report the synthesis, redox and photo-physical properties, as well as singlet oxygen reactivity of the first representatives of Group III perfluoroalkyl perfluoro metal phthalocyanines, gallium and indium complexes. Microwave-assisted synthesis was used to produce F[Formula: see text]PcM, M [Formula: see text] Ga, In in reasonable yields. Both Ga and In complexes exhibit high thermal and chemical stability properties, attributed to the perfluoroalkyl perfluoro phthalocyanine ligand. Electrochemical and spectroelectrochemical measurements show reversible redox processes for both compounds, including spontaneous re-oxidations following electrochemical or photochemical reductions. No electrochemical or chemical oxidations of the neutral complexes are observed. Photo-hydroperoxidation of ([Formula: see text]-(-)-citronellol occurs with rates of 13.5 and 1.7 [Formula: see text]mol O2 min[Formula: see text] mol[Formula: see text] Pc and substrate turnovers of 225 and 28.2 mmol ([Formula: see text]-Cit s[Formula: see text] mol[Formula: see text] Pc for the In and Ga complexes, respectively. The solid state materials are stable and can be sublimed at temperatures higher than 380°C. Related complexes are candidates for similar chemistry and photophysics based on the observation that the fluorinated ligand determines most of the favorable properties.

Photoreactive Superhydrophobic Organic–Inorganic Hybrid Materials Composed of Poly(vinylidene fluoride) and Titanium Dioxide-Supported Perfluorinated Phthalocyanines

“…The bulky, iso-C 3 F 7 substituents of F 64 PcZn (shown as van der Waals spheres in Figure b) preclude π–π stacking in solution, in the solid-state (crystals) and when F 64 PcZn is deposited on supports. , This stacking deactivates the excited state. The UV–vis traces of the MO solutions subjected to broad spectrum light illumination in the presence of (F 64 PcZn∪TiO 2 &NH 4 HCO 3 )∈PVDF and (TiO 2 &NH 4 HCO 3 )∈PVDF coated slides are shown in Figure S5.…”

“…Fluorinated phthalocyanine, F 64 PcZn (Figure 2), was prepared from zinc acetate and perfluoro-(4,5-diisopropyl)phthalonitrile as described previously. 10,11 Instruments. Contact angles (θ°) were measured with a RAMA-HART goniometer by using the sessile water drop method (5 μL drop volume).…”

“…MO solutions were filtered through 0.45 μm cellulose filters. Fluorinated phthalocyanine, F 64 PcZn (Figure ), was prepared from zinc acetate and perfluoro-(4,5-diisopropyl)­phthalonitrile as described previously. , …”

“…8,9 A class of bio-inspired organic photosensitizers that survive electrophilic, nucleophilic, and radical attacks has been reported, their refractory properties being imparted by the presence of C−F bonds. 10,11 The prototypical molecule is zinc 1,4,8,11,15,18,22,25-octakisfluoro-2,3,9,10,16,17,23,24-octakisperfluoro(isopropyl)phthalocyanine, abbreviated F 64 PcZn, shown in Figure 1. Importantly, this class of molecules has frontier orbital energy gaps that remain relatively constant with modifications of the fluorinated substituents, thus allowing structural variations without significant shifts in their Q-band light absorption, which occurs in the 600−800 nm visible− NIR region.…”

“…Inorganic photosensitizers, for example TiO 2 , resist oxidation, , but TiO 2 exhibits a wide band gap requiring UV light for the creation of reactive electron–hole pairs, while also exhibiting an unfavorable fast recombination rate of the charge carriers. , Sustained efforts have been made to narrow the TiO 2 band gap via doping, , but the absorption of energy has not been shifted significantly toward the visible–NIR region of the solar spectrum, where most of the energy of solar radiation is concentrated . Organic photosensitizers such as Rose Bengal produce another oxidant, singlet molecular delta oxygen, 1 Δ g 1 O 2 , from its triplet ground state, 3 Σ g 3 O 2 , but are susceptible to attack and degradation by the reactive oxygen species they produce. , A class of bio-inspired organic photosensitizers that survive electrophilic, nucleophilic, and radical attacks has been reported, their refractory properties being imparted by the presence of C–F bonds. , The prototypical molecule is zinc 1,4,8,11,15,18,22,25-octakis­fluoro-2,3,9,10,16,17,23,24-octakis­perfluoro­(isopropyl)­phthalocyanine, abbreviated F 64 PcZn, shown in Figure . Importantly, this class of molecules has frontier orbital energy gaps that remain relatively constant with modifications of the fluorinated substituents, thus allowing structural variations without significant shifts in their Q-band light absorption, which occurs in the 600–800 nm visible–NIR region. − The enhanced chemical robustness is due to the aliphatic perfluoroalkyl groups, not present in either the all-aromatic F 16 Pc scaffold, susceptible to electron loss and nucleophilic attack, or the parent H 16 Pc molecule that contains weaker C–H bonds.…”