Synthesis and Characterization of Soluble Octaaryl‐ and Octaaryloxy‐Substituted Metal‐Naphthalocyanines

Abstract

An easy route for the synthesis of vanadium, zinc, magnesium, etc. complexes of new soluble symmetrical octa(m-trifluoromethylphenyl) or octa(m-trifluoromethylphenoxy) substituted 2,3-naphthalocyanines {[(m-CF 3 Ph) 8 NcM] or [(m-CF 3 PhO) 8 NcM]} in good yields is described in detail. The structures of the synthesized compounds were verified by UV/Vis and 1 H and 13 C NMR spectroscopy, as well as by mass spectrometry. The good solubilities of the prepared compounds in toluene and coordinating solvents (e.g., THF), was explained in terms of the nonplanar arrangements of eight m-CF 3 Ph substituents in relation to the Nc macrocycle, preventing aggregation of the molecules. The Q-bands in the

Synthesis and Some Properties of Aryl‐ and Aryloxy‐Substituted Phthalocyanines and Their Metal Complexes: A Comparison with Porphyrazine and Naphthalocyanine Analogues

“…In the case of indium naphthalocyanine analogues, their decomposition was considerably faster, so we could not isolate them in pure state. [15] As was also found for other soluble indium phthalocyanines, such as tetra(alkenyloxy)phthalocyaninato(chloro)indium complexes, they also exhibit a tendency to decompose in solution, but are highly stable when incorporated into solid polymer films, [25] which permits their utilization for different applications in this state. This might also apply to the described indium compounds 7a and 7b.…”

“…They exhibit lowfield shifts when, for example, 6a and 7a are compared (150.3 and 136.3 ppm for 6a and 154.7 and 137.8 ppm for 7a respectively). In contrast, their positions in magnesium phthalocyanine 5b and the naphthalocyanine (m-CF 3 PhO) 8 NcMg analogue [15] are almost the same (δ ϭ 152.7, 137.0 and 153.4 and 136.9 ppm respectively), indicating no strong electron redistribution in the centre of the phthalocyanine macrocycle upon symmetrical benzo-annulation. In contrast, on going from indium phthalocyanine 7a to indium porphyrazine [(m-CF 3 Ph) 8 PzIn(Cl)], the electron redistribution is more obvious and results in an increasing electron density in the centre of the porphyrazine macrocycle with benzo-annulation.…”

“…[11,26] 13 C NMR spectra, showing good resolution, and signal assignments for indium phthalocyanines 7a and 7b are given for comparison in Figure 5. In contrast to 6a, the inner carbon atoms in 7a give sharp signals.…”

“…13 C NMR spectra of indium phthalocyanines 7b in CDCl 3 (upper) and 7a in [D 8 ]THF (lower); the signal assignment (see Scheme 3) is based on results of previous work [11,15]  156.6 and 143.0 ppm, respectively. [11] However, the position of carbon resonance C-9 (quadruplet with splitting constant 2 J ഠ 32Ϫ33 Hz) was found to be almost independent of the nature of central metal, macrocycle or solvent in the series of m-CF 3 Ph (δ ϭ 131.2Ϫ131.5 ppm) and m-CF 3 PhO ( δ ϭ 132.6Ϫ133.1) substituted compounds, as would be expected.…”

Fluorinated Naphthalocyanines Displaying Simultaneous Reverse Saturable Absorption at 532 and 1064 nm

“…In toluene, the Q-band of 2c is redshifted to 813 nm with respect to (m-CF 3 PhO) 8 -NcInCl (an analogue of 2c with a less-extended p-conjugation which shows the Q-band at 800.0 nm). [21,22] When compared to (m-CF 3 PhO) 8 NcInCl, [23] 2c shows a higher photostability due to the fluorine substituents. In fact, in oxygen-free solutions F 8 O 8 NcInCl (2c) showed no evidence of optical degradation in quartz cells under light exposure for more than 150 h. Under analogous conditions the alkoxy-substituted (m-CF 3 PhO) 8 NcInCl had a 50 % diminution of the Q-band absorption peak after 60 h. The new precursor 1, reported here and used for the syntheses of Ncs 2b, 2c, and 3, was obtained from the reaction of 3,5-di-tert-butylcatechol (4) with 1,2-dicyano-4,5,6,7-tetrafluoronaphthalene (5) in dimethyl sulfoxide (DMSO) [11] (Scheme 2, see Experimental).…”