| Synthesis and application of phthalocyanines are one of the hotspot in organic chemistry. In this paper, eight novel perfluoroalkyl metallophthalocyariine derivatives were designed and synthesized. In addition, their properties such as absorption and emission, DNA photocleaving ability, photodamage on tumor cells in vitro, fluorous phase catalytic action, photoelectric properties, and applications in printing ink were studied.The derivatives of perfluorobutyl metallophthalocyanines and perfluorohexyl metallophthalocyanines were synthesized from perfluoroalkyl phthalonitrile by means of baking process, and the reaction conditions of which was optimized and Soxlet extracting was used to purified the target compounds. The structures of designed compounds were characterized by 1H NMR, IR, HRMS.UV-vis and fluorescence spectra of fluoroalkyl metallophthaolcyanines (FMPcs) were investigated. The maximum absorption (λmax) wavelengths of FMPcs were at 650-690 nm,λmax of FMPcs were at 590-610 nm in perfluorooctane. All of the maximum wavelength of absorption and emission were blue-shifted with the increasing of solvent polarity in the common organic solvents. The maximum absorption wavelengths of FMPcs were blue-shifted compared with those of unsubstituted complexes. Compared with common organic solvents, blue shift value of the maximum absorption wavelength was larger in perfluorooctane, In addition, the blue-shift of fluorobutyl metalphthalocyanine (FBMPc) was lower than that of fluorohexyl metalphthalocyanine (FHMPc),15-30 nm can be observed; however, the maximum emission wavelength was red-shifted, and the red-shift of the maximum emission wavelength of FHMPc was larger than that of FBMPc,15 nm can be observed. In fluorocarbon solvent perfluoroocane, FMPcs solute molecules were enclosed by perfluoroocane solvent molecules that formed fluorocarbon solvent cage. Fluorocarbon solvent cage and its lagging effect influenced the geometrical and energy variations between the ground state and the excited state of solute molecule of FMPcs and further resulted in the special change of the particular spectral characteristics. The term "Fluorocarbon solvent cage" was established to explain clearly and easily the particular change of absorption and emission spectra in perfluoroocane.The DNA photocleaving ability of perfluoroalkyl metallophthalocyanines was investigated. The results showed that phthalocyanines derivatives which complexed with zinc possess certain photocleaving ability, but the ability of derivatives complex with cobalt,copper and iron was not obvious, which was consistent with fluorescence quantum yield(Φ).The photodynamic activities of zinc (Ⅱ) tetra (perfluoroalkyl) phthalocyanine on HL60 human acute promyelocytic leukemia cell and A375 cancer cell in vitro were investigated. The result showed that the photodynamic effect was obvious when using ZnPc 3b as a photosensitizer, the viability of the HL-60 cell was 50.4% at 100μg/mL after 24 h irradiation.Perfluoroalkyl metallophthalocyanines were used as catalyst under fluorous biphase conditions. The oxidation reaction of ethyl benzene, the oxidation reaction of benzyl alcohol arid chlorination reaction of pyridine were studied. Using tetra (perfluorohexyl) phthalocyanine Cobalt as the catalyst, the conversion of ethylbenzene was 34.6%, the selectivity of acetophenone was 85.4%, the selectivity of phenyl ethyl alcohol was 14.6%; Using tetra-(perfluorobutyl) phthalocyanine Iron as the catalyst, the conversion of benzyl alcohol was 6.4%, the selectivity of benzaldehyde was 100%.In addition, cobalt and copper tetra (perfluoroalkyl) phthalocyanines were selected to be used as full solid dyes for sensitive solar battery and the pigmentation. The photoelectric property of cobalt and copper derivatives and the tinctorial power and luster of copper derivative used for printing ink were carried out.
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