Synthesis and Structure of a Biconcave Cobalt Perfluorophthalocyanine and Its Catalysis of Novel Oxidative Carbon-Phosphorus Bonds Formation by Using Air

Abstract

One of the major challenges of modern chemistry, homogeneous aerobic oxidations, poses the additional challenge of designing suitable catalysts that are not only active, but resist self-oxidation as well. For transition metal complexes, this of 3, a dose of 5 mmol kg À1 induced 60 % regression. [18] These results suggest that the introduction of bulky perfluoroalkyl groups results in higher tumor regression at lower photosensitizer doses; the molecular and pharmacological reasons for the differences between 2 and 3 in vivo remain to be elucidated.In summary, our results provide a simple (classical) yet efficient approach to nonplanar perhalogenated phthalocyanines, of which [F 64 PcZn] is only the first representative. Other metals and R F groups will yield compounds with a diversity of size, shape, and depth of fluorinated cavities around a reactive metal center. Their thermal, photochemical, and chemical stability, coupled with their potential synthetic versatility and favorable solubility, suggest that this class of molecules might be effective for photophysical, chemical, and perhaps, medical uses. Applications requiring stability under harsh conditions and/or aggressive reagents, or solubility in nonconventional solvents might be considered. Experimental Section2: A mixture of zinc acetate (0.123 g, 0.668 mmol) and 1, (1.337 g, 2.67 mmol) was heated under Ar at 180 8C for 60 min. Chromatography on silica gel using 20 ± 30 % acetone/hexanes, followed by diffusion of hexanes into an acetone solution gave crystalline 2 in 21 % yield; m.p. > 300 8C; FAB MS [m/z] 2064.84 [M ]. Elemental analysis: calcd (%) for 13 C NMR (100.613 mHz, [D 6 ]acetone): d 154.6, 152.0, 130.9, 121.5, 117.5, 95.2. UV/Vis [nm] (log e), acetone, 322 (4.38), 396 (4.56), 620 (4.42), 686 (5.24).Biological tests: Suspensions of 2 or 3 in 10 % CRM (CRM cremofor) were administered intravenously. The tumors were illuminated with 650 ± 700 nm light (1 kW Xenon lamp, LL650 and LS700 filters) at fluence rates of 200 mW cm À2 , 400 J cm À2 per tumor. Absence of a palpable tumor three weeks post irradiation was considered regression.

Enhanced Acidity, Photophysical Properties and Liposome Binding of Perfluoroalkylated Phthalocyanines Lacking C‐H Bonds

“…Note in this context that the enhanced solubility imparted to Pcs by perfluoroisopropyl groups, combined with the three‐dimensionality of the new molecules (Fig. 1), allowed atomic‐level single crystal X‐ray data for any halogenated phthalocyanine to be obtained for the first time (21, 22).…”

“…Specifically, starting with a R‐CH 3 moiety, two halogen atoms are used to remove two hydrogen atoms to form a R‐CH=P bond. F 64 PcCo catalyzes the removal of these hydrogen atoms, catalytically, as water, with air (22). Thus, understanding the properties of the coordinating nitrogen atoms of F 64 PcH 2 could provide a better perception of the chemistry of this and other ligand‐metal complexes.…”

Introduction of Bulky Perfluoroalkyl Groups at the Periphery of Zinc Perfluorophthalocyanine: Chemical, Structural, Electronic, and Preliminary Photophysical and Biological Effects

“…A favorable packing may be more important in the solid‐state. The same electronic and steric factors stabilize acetone in the analogous paramagnetic cobalt complex6 and make acetone competitive with O 2 for the copper site in fluorinated tris(pyrazolyl)borate complexes 7. Unlike 2 , the strictly planar zinc perfluorophthalocyanines [F 16 PcZn] ( 3 ; of similar electronic structure, R 1 =R 2 =F in Scheme )8 and protio PcZn9 do not retain solvent when precipitated from acetone.…”

“…This latter notion is in line with the classical view of the inductive effect, whereby electronic influences progressively decrease as the chain is elongated. Considering the potential versatility of Scheme and demonstrated ring planarity of 2 and its cobalt analogue,6 this generalization may be valuable as a synthetic strategy.…”

Synthesis of Phthalocyanines with a Pentafluorosulfanyl Substituent at Peripheral Positions

“…Fluoro‐functionalized Pcs have thus emerged as lipophilic and stabilized Pcs to overcome these shortfalls . These fluorinated Pcs are also expected to exhibit novel and unique properties, and trifluoroethoxy‐Pcs and perfluoroisopropyl Pc, are two representative examples of this compound class. Many reports have documented the synthesis of Pcs having fluorinated functional groups on peripheral positions but there is no example of the synthesis of Pcs having an SF 5 moiety directly in their peripheral positions .…”